DE19815275B4 - Alkylidene complexes of ruthenium with N-heterocyclic carbene ligands and their use as highly active, selective catalysts for olefin metathesis - Google Patents

Alkylidene complexes of ruthenium with N-heterocyclic carbene ligands and their use as highly active, selective catalysts for olefin metathesis Download PDF

Info

Publication number
DE19815275B4
DE19815275B4 DE19815275A DE19815275A DE19815275B4 DE 19815275 B4 DE19815275 B4 DE 19815275B4 DE 19815275 A DE19815275 A DE 19815275A DE 19815275 A DE19815275 A DE 19815275A DE 19815275 B4 DE19815275 B4 DE 19815275B4
Authority
DE
Germany
Prior art keywords
radicals
carbon atoms
cyclic
different
groups
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
DE19815275A
Other languages
German (de)
Other versions
DE19815275A1 (en
Inventor
Wolfgang Anton Prof. Dr. Herrmann
Wolfgang Dr. Schattenmann
Thomas Weskamp
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Evonik Degussa GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=7863687&utm_source=***_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=DE19815275(B4) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Evonik Degussa GmbH filed Critical Evonik Degussa GmbH
Priority to DE19815275A priority Critical patent/DE19815275B4/en
Priority to DE59912097T priority patent/DE59912097D1/en
Priority to EP99910357A priority patent/EP1087838B1/en
Priority to PCT/EP1999/001785 priority patent/WO1999051344A1/en
Priority to US09/647,742 priority patent/US6635768B1/en
Priority to JP2000542103A priority patent/JP4531253B2/en
Priority to IL13859599A priority patent/IL138595A/en
Publication of DE19815275A1 publication Critical patent/DE19815275A1/en
Priority to US10/630,552 priority patent/US7294717B2/en
Priority to US11/021,967 priority patent/US7652145B2/en
Priority to US11/828,828 priority patent/US7378528B2/en
Priority to US12/115,139 priority patent/US20080207911A1/en
Publication of DE19815275B4 publication Critical patent/DE19815275B4/en
Application granted granted Critical
Priority to US13/090,688 priority patent/US8153810B2/en
Priority to US14/193,785 priority patent/US20150038723A1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2269—Heterocyclic carbenes
    • B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
    • C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/475—Preparation of carboxylic acid esters by splitting of carbon-to-carbon bonds and redistribution, e.g. disproportionation or migration of groups between different molecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
    • B01J2231/14—Other (co) polymerisation, e.g. of lactides, epoxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
    • B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0261—Complexes comprising ligands with non-tetrahedral chirality
    • B01J2531/0263—Planar chiral ligands, e.g. derived from donor-substituted paracyclophanes and metallocenes or from substituted arenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/24—Phosphines

Abstract

Komplexverbindung des Rutheniums der allgemeinen-Strukturformel I,

Figure 00000001
in der X1 und X2 gleich oder verschieden voneinander einen anionischen Liganden bedeuten,
in der R1 und R2 gleich oder unabhängig voneinander verschieden sind, aber auch einen Cyclus auf weisen können,
in der R1 und R2 für Wasserstoff oder/und für eine Kohlenwasserstoffgruppe stehen,
wobei die Kohlenwasserstoffgruppen gleich oder unabhängig voneinander verschieden aus geradkettigen, verzweigten, cyclischen oder/und nicht cyclischen Resten aus der Gruppe von Alkylresten mit 1 bis 50 Kohlenstoffatomen, Alkenylresten mit 1 bis 50 Kohlenstoffatomen, Alkinylresten mit 1 bis 50 Kohlenstoffatomen, Arylresten mit 1 bis 30 Kohlenstoffatomen und Silylresten bestehen,
wobei in den Kohlenwasserstoff- oder/und Silylgruppen die Wasserstoffatome teilweise oder gänzlich durch eine Alkyl-, Aryl-, Alkenyl-, Alkinyl-, Metallocenyl-, Halogen-, Nitro-, Nitroso-, Hydroxy-, Alkoxy-, Aryloxy-, Amino-, Amido-, Carboxyl-, Carbonyl-, Thio- oder/und Sulfonylgruppe einfach oder mehrfach, gleich oder unabhängig voneinander verschieden ersetzt sein können,
in der der Ligand L1 ein N-heterozyklisches Carben...Complex compound of ruthenium of the general structural formula I,
Figure 00000001
in which X 1 and X 2 are identical or different and denote an anionic ligand,
in which R 1 and R 2 are the same or different, but may also have a cycle,
in which R 1 and R 2 are hydrogen or / and a hydrocarbon group,
wherein the hydrocarbon groups are identical or independently different from straight-chain, branched, cyclic or / and non-cyclic radicals from the group of alkyl radicals having 1 to 50 carbon atoms, alkenyl radicals having 1 to 50 carbon atoms, alkynyl radicals having 1 to 50 carbon atoms, aryl radicals having 1 to 30 Carbon atoms and silyl radicals exist,
wherein in the hydrocarbon or / and silyl groups, the hydrogen atoms are partially or wholly represented by an alkyl, aryl, alkenyl, alkynyl, metallocenyl, halogen, nitro, nitroso, hydroxy, alkoxy, aryloxy, amino -, amido, carboxyl, carbonyl, thio or / and sulfonyl group may be monosubstituted or polysubstituted, the same or independently different,
in which the ligand L 1 forms an N-heterocyclic carbene ...

Description

Die Erfindung betrifft Alkylidenkomplexverbindungen des Rutheniums mit N-heterozyklischen Carbenliganden und ein Verfahren zur Herstellung von Olefinen durch Olefin-Metathese aus acyclischen Olefinen mit zwei oder mehr Kohlenstoffatomen oder/und aus cyclischen Olefinen mit vier oder mehr Kohlenstoffatomen, wobei mindestens eine dieser Alkylidenkomplexverbindungen als Katalysator eingesetzt wird.The The invention relates to alkylidene complexes of ruthenium with N-heterocyclic carbene ligands and a method of preparation of olefins by olefin metathesis of acyclic olefins with two or more carbon atoms or / and from cyclic olefins with four or more carbon atoms, wherein at least one of these Alkylidenkomplexverbindungen is used as a catalyst.

Übergangsmetallkatalysierte C-C-Verknüpfungen gehören zu den wichtigsten Reaktionen der organischen Synthesechemie. in diesem Zusammenhang stellt die Olefin-Metathese einen wesentlichen Bestandteil dar, da mittels dieser Reaktion nebenproduktfrei Olefine synthetisiert werden können. Die Olefin-Metathese besitzt dabei nicht nur hohes Potential auf dem Sektor der präparativen, organischen Synthese (RCM, Ethenolyse, Metathese acyclischer Olefine), sondern auch in der Polymerchemie (ROMP, ADMET, Alkinpolymerisation). Seit ihrer Entdeckung in den 50er Jahren konnten mehrere großtechnische Prozesse realisiert werden. Dennoch avancierte die Olefin-Metathese erst in jüngster Zeit durch die Entdeckung neuer Katalysatoren zu einer breit anwendbaren Synthesemethode (J. C. Mol in: B. Cornils, W. A. Herrmann: Applied Homogeneous Catalysis with Organometallic Compounds, VCH, Weinheim, 1996, S. 318–332; M. Schuster, S. Blechert, Angew. Chem. 1997, 109, 2124–2144; Angew. Chem. Int. Ed. Engl. 1997, 36, 2036–2056).Transition-metal C-C-links belong to the most important reactions of organic synthetic chemistry. in In this context, the olefin metathesis provides a substantial Component, because by means of this reaction by-product olefins can be synthesized. The olefin metathesis not only has high potential here the sector of preparative, organic synthesis (RCM, ethenolysis, metathesis of acyclic olefins), but also in polymer chemistry (ROMP, ADMET, alkyne polymerization). Since their discovery in the 50s, several large-scale Processes are realized. Nevertheless, olefin metathesis advanced only recently Time through the discovery of new catalysts to a widely applicable Synthesis method (J.C.Mol in: B. Cornils, W.A. Herrmann: Applied Homogeneous Catalysis with Organometallic Compounds, VCH, Weinheim, 1996, pp. 318-332; M. Schuster, S. Blechert, Angew. Chem. 1997, 109, 2124-2144; Angew. Chem. Int. Ed. Engl. 1997, 36, 2036-2056).

Zahlreiche, grundlegende Arbeiten haben wesentlich zum Verständnis dieser übergangsmetallkatalysierten Reaktion beigetragen, bei der ein Austausch von Alkylideneinheiten zwischen Olefinen erfolgt. Der allgemein akzeptierte Mechanismus beinhaltet Metallalkylidenkomplexe als aktive Spezien. Diese reagieren mit Olefinen zu Metallacyclobutanintermediaten, die unter Cycloreversion wieder Olefine und Alkylidenkomplexe generieren. Die Isolierung von metatheseaktiven Alkyliden- und Metallacyclobutankomplexen untermauert diese mechanistischen Vorstellungen.numerous, Fundamental work is essential to understanding this transition-metal-catalyzed Reaction contributed to the exchange of alkylidene units between olefins takes place. The generally accepted mechanism includes metal alkylidene complexes as active species. These react with olefins to metallacyclobutane intermediates under cycloreversion again generate olefins and alkylidene complexes. The insulation supported by metathesis-reactive alkylidene and Metallacyclobutankomplexen these mechanistic ideas.

Zahlreiche Beispiele finden sich vor allem in der Komplexchemie des Molybdäns und Wolframs. Speziell durch Arbeiten von Schrock wurden wohldefinierte Alkylidenkomplexe erhalten, die in ihrer Reaktivität kontrollierbar sind (J. S. Murdzek, R. R Schrock, Organometallics 1987, 6, 1373–1374). Die Einführung einer chiralen Ligandsphäre an diesen Komplexen ermöglichte die Synthese von Polymeren mit hoher Taktizität (K. M. Totland, T. J. Boyd, G. C. Lavoie, W. M. Davis, R. R. Schrock, Macromolecules 1996, 29, 6114–6125). Chirale Komplexe gleichen Strukturtyps wurden auch in der Ringschluß-Metathese mit Erfolg eingesetzt (O. Fujimura, F. J. d. I. Mata, R. H. Grubbs, Organometallics 1996, 15, 1865–1871). Nachteilig stellt sich jedoch die hohe Empfindlichkeit gegenüberfunktionellen Gruppen, Luft und Wasser heraus.numerous Examples are found especially in the complex chemistry of molybdenum and tungsten. Especially by Schrock's work, well-defined alkylidene complexes have been synthesized which are controllable in their reactivity (J.S. Murdzek, R. R Schrock, Organometallics 1987, 6, 1373-1374). The introduction a chiral ligand sphere allowed on these complexes the synthesis of polymers with high tacticity (K. M. Totland, T. J. Boyd, G.C. Lavoie, W.M. Davis, R.R. Schrock, Macromolecules 1996, 29, 6114-6125). Chiral complexes of the same structural type were also used in ring-closing metathesis used successfully (O. Fujimura, F.J. d. I. Mata, R.H. Grubbs, Organometallics 1996, 15, 1865-1871). However, the disadvantage is the high sensitivity to functional Groups, air and water out.

In jüngster Zeit haben sich phosphanhaltige Komplexsysteme des Rutheniums etabliert (R. H. Grubbs, S. T. Nguyen, L. K. Johnson, M. A. Hillmyer, G. C. Fu, WO 96/04289 , 1994; P. Schwab, M. B. France, J. W. Ziller, R. H. Grubbs, Angew. Chem., 1995, 107, 2179–2181; Angew. Chem. Int. Ed. Engl. 1995, 34, 2039–2041). Aufgrund des elektronenreichen, "weichen" Charakters später Übergangsmetalle besitzen diese Komplexe eine hohe Toleranz gegenüber harten, funktionellen Gruppen. Dies wird beispielsweise durch ihren Einsatz in der Naturstoffchemie (RCM von Dienen) demonstriert (Z. Yang, Y. He, D. Vourloumis, H. Vallberg, K. C. Nicolaou, Angew. Chem. 1997, 109, 170–172; Angew. Chem., Int. Ed. Engl. 1997, 36, 166–168; D. Meng, P. Bertinato, A. Balog, D. S. Su, T. Kamenecka, E. J. Sorensen, S. J. Danishefsky, J. Am. Chem. Soc. 1997, 119, 2733–2734; D. Schinzer, A. Limberg, A. Bauer, O. M. Böhm, M. Cordes, Angew. Chem. 1997, 109, 543–544; Angew. Chem., Int. Ed. Engl. 1997, 36, 523–524; A. Fürstner, K. Langemann, J. Am. Chem. Soc. 1997, 119, 9130–9136).Phosphine-containing complex systems of ruthenium have recently been established (RH Grubbs, ST Nguyen, LK Johnson, MA Hillmyer, GC Fu, WO 96/04289 , 1994; P. Schwab, MB France, JW Ziller, RH Grubbs, Angew. Chem., 1995, 107, 2179-2181; Angew. Chem. Int. Ed. Engl. 1995, 34, 2039-2041). Due to the electron-rich, "soft" character of late transition metals, these complexes have a high tolerance to hard, functional groups. This is demonstrated, for example, by their use in natural product chemistry (RCM by Dienen) (Z. Yang, Y. He, D. Vourloumis, H. Vallberg, KC Nicolaou, Angew Chem 1997, 109, 170-172; Angew. Chem Ed., Engl. 1997, 36, 166-168; D. Meng, P. Bertinato, A. Balog, DS Su, T. Kamenecka, EJ Sorensen, SJ Danishefsky, J. Am. Chem. Soc., 1997 , 119, 2733-2734; D. Schinzer, A. Limberg, A. Bauer, OM Bohm, M. Cordes, Angew Chem 1997, 109, 543-544; Angew. Chem., Int. Ed. Engl. 1997 , 36, 523-524; A. Fürstner, K. Langemann, J. Am. Chem. Soc. 1997, 119, 9130-9136).

Die Variationsbreite der verwendeten Phosphanliganden ist jedoch aufgrund sterischer und elektronischer Faktoren sehr begrenzt. Lediglich stark basische, sterisch anspruchsvolle Alkylphosphane wie Tricyclohexyl-, Triisopropyl- und Tricyclopentylphosphan eignen sich für die Metathese acyclischer Olefine und wenig gespannter Ringsysteme. Demnach sind diese Katalysatoren nicht in ihrer Reaktivität einstellbar. Auch chirale Komplexe dieses Strukturtyps konnten nicht realisiert werden.The However, the variation of the phosphine ligands used is due to steric and electronic factors very limited. Only strongly basic, sterically demanding alkylphosphines such as tricyclohexyl, Triisopropyl- and tricyclopentylphosphine are suitable for metathesis acyclic olefins and less strained ring systems. Accordingly, they are these catalysts can not be adjusted in their reactivity. Also chiral complexes This type of structure could not be realized.

Aus diesen Gründen bestand die Aufgabe, maßgeschneiderte Metathesekatalysatoren zu entwickeln, die sich neben hoher Toleranz gegenüber funktionellen Gruppen durch eine variable Ligandensphäre auszeichnen und die eine Feineinstellung des Katalysators für spezielle Eigenschaften unterschiedlicher Olefine ermöglichen. Ferner bestand die Aufgabe, ein Verfahren zur Herstellung von Olefinen bereitzustellen, bei dem die Reaktivität einstellbar ist und chirale komplexe realisiert werden können.Out these reasons the task was tailor made To develop metathesis catalysts, in addition to high tolerance across from functional groups characterized by a variable ligand sphere and the fine tuning of the catalyst for special properties different Enable olefins. It was also the object of a process for the preparation of olefins be provided, in which the reactivity is adjustable and chiral complex can be realized.

Die Aufgabe wird erfindungsgemäß gelöst durch eine Komplexverbindung des Rutheniums der allgemeinen Strukturformel I,

Figure 00030001
in der X1 und X2 gleich oder verschieden voneinander einen anionischen Liganden bedeuten,
in der R1 und R2 gleich oder unabhängig voneinander verschieden sind, aber auch. einen Cyclus aufweisen können,
in der R1 und R2 für Wasserstoff oder/und für eine Kohlenwasserstoffgruppe stehen, bei die Kohlenwasserstoffgruppen gleich oder unabhängig voneinander verschieden aus geradkettigen, verzweigten, cyclischen oder/und nicht cyclischen Resten aus der Gruppe von Alkylresten mit 1 bis 50 Kohlenstoffatomen, Alkenylresten mit 1 bis 50 Kohlenstoffatomen, Alkinylresten mit 1 bis 50 Kohlenstoffatomen, Arylresten mit 1 bis 30 Kohlenstoffatomen und Silylresten bestehen,
wobei in den Kohlenwasserstoff- oder/und Silylgruppen die Wasserstoffatome teilweise oder gänzlich durch eine Alkyl-, Aryl-, Alkenyl-, Alkinyl-, Metallocenyl-, Halogen-, Nitro-, Nitroso-, Hydroxy-, Alkoxy-, Aryloxy-, Amino-, Amido-, Carboxyl-, Carbonyl-, Thio- oder/und Sulfonylgruppe einfach oder mehrfach, gleich oder unabhängig voneinander verschieden ersetzt sein können,
in der der Ligand L1 ein N-heterozyklisches Carben der allgemeinen Formeln II–IV ist und in der der Ligand L2 Phosphan, ist,
Figure 00040001
wobei R1', R2', R3' und R4' in den Formeln II, III, IV gleich oder verschieden für Wasserstoff oder/und für Kohlenwasserstoffgruppen stehen,
wobei die Kohlenwasserstoffgruppen aus gleichen oder verschiedenen, cyclischen, nicht cyclischen, geradkettigen oder/und verzweigten Resten aus der Gruppe von Alkylresten mit 1 bis 50 Kohlenstoffatomen, Alkenylresten mit 1 bis 50 Kohlenstoffatomen, Alkinylresten mit 1 bis 50 Kohlenstoffatomen und Arylresten mit 1 bis 30 Kohlenstoffatomen bestehen,
und wobei
gegebenenfalls R3' und R4' für Halogen-, Nitro-, Nitroso-, Alkoxy-, Aryloxy-, Amido-, Carboxyl-, Carbonyl-, Thio- oder/und Sulfonylgruppen einfach oder mehrfach, gleich oder unabhängig voneinander verschieden stehen kann.The object is achieved according to the invention by a complex compound of ruthenium of the general structural formula I,
Figure 00030001
in which X 1 and X 2 are identical or different and denote an anionic ligand,
in which R 1 and R 2 are the same or different, but also different. can have a cycle,
in which R 1 and R 2 are hydrogen or / and a hydrocarbon group, wherein the hydrocarbon groups are identical or independently different from straight-chain, branched, cyclic or / and non-cyclic radicals from the group of alkyl radicals having 1 to 50 carbon atoms, alkenyl radicals with 1 to 50 carbon atoms, alkynyl radicals having 1 to 50 carbon atoms, aryl radicals having 1 to 30 carbon atoms and silyl radicals,
wherein in the hydrocarbon or / and silyl groups, the hydrogen atoms are partially or wholly represented by an alkyl, aryl, alkenyl, alkynyl, metallocenyl, halogen, nitro, nitroso, hydroxy, alkoxy, aryloxy, amino -, amido, carboxyl, carbonyl, thio or / and sulfonyl group may be monosubstituted or polysubstituted, the same or independently different,
in which the ligand L 1 is an N-heterocyclic carbene of the general formulas II-IV and in which the ligand L 2 is phosphine,
Figure 00040001
where R 1 ' , R 2' , R 3 ' and R 4' in the formulas II, III, IV are identical or different and denote hydrogen and / or hydrocarbon groups,
wherein the hydrocarbon groups of identical or different, cyclic, non-cyclic, straight-chain and / or branched radicals from the group of alkyl radicals having 1 to 50 carbon atoms, alkenyl radicals having 1 to 50 carbon atoms, alkynyl radicals having 1 to 50 carbon atoms and aryl radicals having 1 to 30 carbon atoms consist,
and where
optionally R 3 ' and R 4' for halogen, nitro, nitroso, alkoxy, aryloxy, amido, carboxyl, carbonyl, thio or / and sulfonyl groups can be mono- or polysubstituted, identical or independently different ,

Die erfindungsgemäßen Komplexverbindungen sind hochaktive Katalysatoren für die Olefin-Metathese. Sie sind besonders kostengünstig. Die Olefin-Metathese mit den erfindungsgemäßen Katalysatoren zeichnet sich neben einer hohen Toleranz gegenüber unterschiedlichsten funktionellen Gruppen auch durch ihre Variationsvielfalt in der Ligandensphäre aus. Durch Variation der präparativ einfach zugänglichen N-heterozyklischen Carbenliganden können Aktivität und Selektivität gezielt gesteuert, und darüber hinaus kann Chiralität auf einfache Art und Weise eingeführt werden.The complex compounds according to the invention are highly active catalysts for the olefin metathesis. They are particularly inexpensive. The olefin metathesis with the catalysts of the invention is characterized by a high tolerance to the most diverse functional Groups also by their Variation variety in the ligand sphere. By variation of the preparative easily accessible N-heterocyclic carbene ligands can target activity and selectivity controlled, and above In addition, chirality can occur simple way introduced become.

Vorzugsweise sind die anionischen Liganden X1 und X2 der erfindungsgemäßen Komplexverbindung gleich oder verschieden Halogenid, Pseudohalogenid, Tetraphenylborat, perhalogeniertes Tetraphenylborat, Tetrahalogenoborat, Hexahalogenophosphat, Hexahalogenoantimonat, Trihalogenomethansulfonat, Alkoxid, Carboxylat, Tetrahalogenoaluminat, Tertracarbonyl-Cobaltat, Hexahalogenoferrat(III), Tetrahalogenoferrat(III) oder/und Tetrahalogenopalladat(II), wobei Halogenid, Pseudohalogenid, Tetraphenylborat, perfluoriertes Tetraphenylborat, Tetrafluoroborat, Hexafluorophosphat, Hexafluoroantimonat, Trifluormethansulfonat, Alkoxid, Carboxylat, Tetrachloroaluminat, Tertracarbonyl-Cobaltat, Hexafluoroferrat(III), Tetrachloroferrat(III) oder/und Tetrachloropalladat(II) bevorzugt sind und wobei unter den Pseudohalogeniden Cyanid, Rhodanid, Cyanat, Isocyanat, Thiocyanat und Isothiocyanat bevorzugt sind.Preferably, the anionic ligands X 1 and X 2 of the complex compound according to the invention are identical or different halide, pseudohalide, tetraphenylborate, perhalogenated tetraphenylborate, tetrahalogenoborate, hexahalogenophosphate, hexahalogenoantimonate, Trihalogenomethansulfonat, alkoxide, carboxylate, tetrahaloaluminate, Tertracarbonyl cobaltate, hexahalogenoferrate (III), tetrahalogenoferrate ( III) or / and tetrahalogenopalladate (II), halide, pseudohalide, tetraphenylborate, perfluorinated tetraphenylborate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, trifluoromethanesulfonate, alkoxide, carboxylate, tetrachloroaluminate, tetracarbonyl cobaltate, hexafluoroferrate (III), tetrachloroferrate (III) or / and Tetrachloropalladate (II) are preferred and wherein among the pseudohalides cyanide, rhodanide, cyanate, isocyanate, thiocyanate and isothiocyanate are preferred.

In den allgemeinen Formeln II, III, IV kann der Wasserstoff in den Kohlenwasserstoffgruppen R1', R2', R3' und R4' teilweise oder gänzlich durch Halogen-, Nitro-, Nitroso-, Hydroxy-, Alkoxy-, Aryloxy-, Amino-, Amido-, Carboxyl-, Carbonyl-, Thio-, Sulfonyl- oder/und Metallocenylgruppen einfach oder mehrflach, gleich oder unabhängig voneinander verschieden ersetzt sein. In diesen Formeln kann R3' und R4' ein anneliertes Ringsystem darstellen.In the general formulas II, III, IV, the hydrogen in the hydrocarbon groups R 1 ' , R 2' , R 3 ' and R 4' may be partially or entirely substituted by halogen, nitro, nitroso, hydroxy, alkoxy, aryloxy -, amino, amido, carboxyl, carbonyl, thio, sulfonyl or / and metallocenyl be monosubstituted or mehrflach, the same or independently substituted differently. In these formulas, R 3 ' and R 4' may be a fused ring system.

Die Liganden L1 und L2 der Komplexverbindung der allgemeinen Strukturformel I können einen Chelatliganden der allgemeinen Former V L1-Y-L2 Vausbilden, wobei L1 ein N-heterocyclisches Carbon der allgemeinen Formell II ist, wobei die mit Y bezeichneten Brückenglieder aus cyclischen, nicht cyclischen, geradkettigen oder/und verzweigten Resten aus der Gruppe von Alkylenresten mit 1 bis 50 Kohlenstoffatomen, Alkenylenresten mit 1 bis 50 Kohlenstoffatomen, Alkinylenresten mit 1 bis 50 Kohlenstoffatomen, Arylenresten mit 1 bis 30 Kohlenstoffatomen, Metallocenylen-, Borylen- und Silylenresten bestehen können, bei denen gegebenenfalls mindestens ein Wasserstoff durch Alkyl-, Aryl-, Alkenyl-, Alkinyl-, Metallocenyl-, Halogen-, Nitro-, Nitroso-, Hydroxo-, Alkoxy-, Aryloxy-, Amino-, Amido-, Carboxyl-, Carbonyl-, Thio- oder/und Sulfonylgruppen, bevorzugt durch Alkyl-, Aryl- oder/und Metallocenylgruppen einfach oder mehrfach, gleich oder unabhängig voneinander verschieden substituiert sein kann.The ligands L 1 and L 2 of the complex compound of the general structural formula I can be a chelate ligand of the general formers V L 1 -YL 2 V wherein L 1 is an N-heterocyclic carbon of the general formula II, wherein the bridge members denoted by Y from cyclic, non-cyclic, straight-chain and / or branched radicals from the group of alkylene radicals having 1 to 50 carbon atoms, alkenylene radicals having 1 to 50 Carbonyl, alkynylene radicals having from 1 to 50 carbon atoms, arylene radicals having from 1 to 30 carbon atoms, metallocenylene, borylene and silylene radicals in which optionally at least one hydrogen is substituted by alkyl, aryl, alkenyl, alkynyl, metallocenyl, halogen , Nitro, nitroso, hydroxo, alkoxy, aryloxy, amino, amido, carboxyl, carbonyl, thio or / and sulfonyl groups, preferably by alkyl, aryl or / and metallocenyl groups singly or multiply, may be substituted differently or independently of one another.

Vorzugsweise weisen die Alkylreste, Alkenylreste, Alkinylreste bzw. die Alkylenreste, Alkenylenreste, Alkinylenreste in den Formeln I bis VI 1 bis 20 Kohlenstoffatome, besonders bevorzugt 1 bis 12 Kohlenstoffatome, auf.Preferably the alkyl radicals, alkenyl radicals, alkynyl radicals or the alkylene radicals, Alkenylene, Alkinylenreste in the formulas I to VI 1 to 20 Carbon atoms, more preferably 1 to 12 carbon atoms, on.

Die Liganden der allgemeinen Formeln II, III, IV, oder/und V können zentrale, axiale oder/und planare Chiralität aufweisen.The Ligands of the general formulas II, III, IV, or / and V can be central, axial and / or planar chirality exhibit.

In der aligemeinen Strukturformel I der Komplexverbindung stehen R1 bis R2 bevorzugt für Wasserstoff, substituierte oder/und nichtsubstituierte Alkyl-, Alkenyl- oder/und Arylreste, X1 und X2 bevorzugt für Halogenid-, Alkoxid- oder/und Carboxylationen sind und L1 bevorzugt für ein N-heterozyklisches Carben der allgemeinen Formel II steht.In general structural formula I of the complex compound, R 1 to R 2 are preferably hydrogen, substituted or / and unsubstituted alkyl, alkenyl or / and aryl radicals, X 1 and X 2 are preferably halide, alkoxide and / or carboxylate ions and L 1 is preferably an N-heterocyclic carbene of the general formula II.

Die Synthese der Komplexe erfolgt üblicherweise durch Ligandsubstitution entsprechender Phosphankomplexe. Diese können entsprechend Reaktionsgleichung (1) selektiv zweifach oder entsprechend Reaktionsgleichung (2) einfach substituiert werden. Im Fall der einfachen Substitution kann das zweite Phosphan selektiv durch einen anderen Elektronendonor, z. B. Pyridin, Phosphan, N-Heterozyklencarben, Phosphit, Stibin, Arsin substituiert werden entsprechend Reaktionsgleichung (3).The Synthesis of the complexes usually takes place by ligand substitution of corresponding phosphine complexes. These can according to reaction equation (1) selectively twice or correspondingly Reaction equation (2) are easily substituted. In the case of simple substitution, the second phosphine can be selectively replaced by a another electron donor, z. Pyridine, phosphine, N-heterocyclic carbene, Phosphite, stibine, arsine are substituted according to reaction equation (3).

Insbesondere gelingt auf diesem Weg die erstmalige Darstellung von chiralen, metatheseaktiven Katalysatoren auf Rutheniumbasis (Komplexbeispiele 2 und 3).Especially succeeds in this way the first presentation of chiral, ruthenium-based metathesis-active catalysts (complex examples 2 and 3).

Figure 00060001
Figure 00060001

Die erfindungsgemäßen Komplexverbindungen erweisen sich als äußerst effiziente. Katalysatoren in der Olefin-Metathese. Die ausgezeichnete Metatheseaktivität wird durch mehrere Beispiele verschiedener metathetischer Reaktionen in den Beispielen demonstriert.The complex compounds according to the invention prove to be extremely efficient. Catalysts in olefin metathesis. The excellent metathesis activity is going through several examples of different metathetic reactions in the Examples demonstrated.

Deshalb umfaßt diese Erfindung auch die Verfahren aller Olefin-Metathese-Reaktionen wie Ringöffnende Metathesepolymerisation (ROMP), Metathese acyclischer Olefine, Ethenolyse, Ringschlußmetathese (RCM), acyclische Dien-Metathese-Polymerisation (ADMET) und Depolymerisatfon olefinischer Polymere. Die hohe Stabilität und Toleranz der erfindungsgemäßen Komplexverbindungen gegenüber funktionellen Gruppen, insbesondere Gruppen von Alkoholen, Aminen, Thiolen, Ketonen, Aldehyden, Carbonsäuren, Estern, Amiden, Ethern, Silanen, Sulfiden und Halogenen erlaubt die Anwesenheit derartiger funktioneller Gruppen während der Metathesereaktion.Therefore comprises this invention also covers the processes of all olefin metathesis reactions, such as ring-opening Metathesis polymerization (ROMP), metathesis of acyclic olefins, ethenolysis, Ring-closing metathesis (RCM), acyclic diene-metathesis polymerization (ADMET) and Depolymerisatfon olefinic polymers. The high stability and tolerance the complex compounds of the invention across from functional groups, in particular groups of alcohols, amines, Thiols, ketones, aldehydes, carboxylic acids, esters, amides, ethers, Silanes, sulfides and halogens allow the presence of such functional groups during the metathesis reaction.

Die Aufgabe wird ferner durch ein Verfahren zur Herstellung von acyclischen Olefinen mit zwei oder mehr Kohlenstoffatomen oder/und von cyclischen Olefinen mit vier oder mehr Kohlenstoffatomen jeweils entsprechend der allgemeinen Formel VI

Figure 00070001
aus acyclischen Olefinen mit zwei oder mehr Kohlenstoffatomen oder/und aus cyclischen Olefinen mit vier oder mehr Kohlenstoffatomen jeweils entsprechend der allgemeinen Formel VI durch Olefin-Metathese-Reaktion in Gegenwart mindestens eines Katalysators gelöst, das dadurch gekennzeichnet ist, daß
ein Katalysator nach einem der Ansprüche 1 bis 7 eingesetzt wird und daß R''1, R''2, R''3 und R''4 der allgemeinen Formel VI für Wasserstoff oder/und I Kohlenwasserstoffgruppen stehen,
wobei die Kohlenwasserstoffgruppe aus gleich oder unabhängig voneinander verschieden geradkettigen, verzweigten, cyclischen oder/und nicht cyclischen Resten aus der Gruppe von Alkylresten mit 1 bis 50 Kohlenstoffatomen, Alkenylresten mit 1 bis 50 Kohlenstoffatomen, Alkinylresten mit 1 bis 50 Kohlenstoffatomen, Arylresten mit 1 bis 30 Kohlenstoffatomen, Metallocenyl- oder/und Silylresten besteht, wobei gegebenenfalls R''1, R''2, R''3 und R''4 für Halogen-, Nitro-, Nitroso-, Hxdroxy-, Alkoxy-, Aryloxy-, Amino-, Amido-, Carbonyl-, Carbonyl-, Thio-, Sulfonyl- oder/und Metallocenylgruppen einfach oder mehrfach, gleich oder unabhängig voneinander verschieden stehen.The object is further achieved by a process for the preparation of acyclic olefins having two or more carbon atoms or / and of cyclic olefins having four or more carbon atoms each corresponding to the general formula VI
Figure 00070001
from acyclic olefins having two or more carbon atoms or / and from cyclic olefins having four or more carbon atoms each corresponding to the general formula VI by olefin metathesis reaction in the presence of at least one catalyst, characterized in that
a catalyst according to any one of claims 1 to 7 is used and that R '' 1 , R '' 2 , R '' 3 and R '' are 4 of the general formula VI are hydrogen or / and I hydrocarbon groups,
wherein the hydrocarbon group of the same or independently different straight-chain, branched, cyclic or / and non-cyclic radicals from the group of alkyl radicals having 1 to 50 carbon atoms, alkenyl radicals having 1 to 50 carbon atoms, alkynyl radicals having 1 to 50 carbon atoms, aryl radicals having 1 to 30 Carbon atoms, metallocenyl or / and silyl radicals, where appropriate R '' 1 , R '' 2 , R '' 3 and R '' 4 are halogen, nitro, nitroso, hydroxy, alkoxy, aryloxy, Amino, amido, carbonyl, carbonyl, thio, sulfonyl or / and metallocenyl groups singly or multiply, the same or independently different.

Vorzugsweise sind in den eingesetzten oder/und in den herzustellenden Olefinen eine oder/und mehrere Doppelbindungen enthalten. Insbesondere bilden R'1, R'2, R'3 und R'4 in den Olefinen der allgemeinen Formel VI paarweise, einfach oder mehrfach, gleich oder unabhängig voneinander verschieden einen Cyclus aus. Vorzugsweise ist in den Olefinen der allgemeinen Formel VI der Wasserstoff in den Kohlenwasserstoffgruppen R''1, R''2, R''3 und R''4 teilweise oder gänzlich durch Halogen-, Silyl-, Nitro-, Nitroso-, Hydroxy-, Alkoxy-, Aryloxy-, Amino-, Amido-, Carboxyl-, Carbonyl-, Thio-, Sulfonyl- oder/und Metallocenylgruppen einfach oder mehrfach, gleich oder unabhängig voneinander verschieden ersetzt.Preferably, one or more double bonds are contained in the olefins used and / or in the olefins to be prepared. In particular, R ' 1 , R' 2 , R ' 3 and R' 4 form in the olefins of general formula VI in pairs, one or more times, the same or independently different from a cycle. Preferably, in the olefins of the general formula VI, the hydrogen in the hydrocarbon groups R " 1 , R" 2 , R " 3 and R" 4 is partly or wholly by halogen, silyl, nitro, nitroso, hydroxy -, alkoxy, aryloxy, amino, amido, carboxyl, carbonyl, thio, sulfonyl or / and Metallocenylgruppen simply or repeatedly, the same or independently different replaced.

Bei dem erfindungsgemäßen Verfahren kann der Prozeß mit oder ohne Lösungsmittel, jedoch vorzugsweise mit organischen Lösungsmitteln, durchgeführt werden. Vorzugsweise kann das erfindungsgemäße Verfahren unter Zusatz einer Brönstedt-Säure, vorzugsweise von HCl, HBr, HI, HBF4, HPF6 oder/und Trifluoressigsäure, oder/und unter Zusatz einer Lewis-Säure, vorzugsweise von BF3, AlCl3 oder/und ZnI2, durchgeführt werden.In the process according to the invention, the process can be carried out with or without solvent, but preferably with organic solvents. The process according to the invention can preferably be carried out with the addition of a Bronsted acid, preferably of HCl, HBr, HI, HBF 4 , HPF 6 or / and trifluoroacetic acid, or / and with the addition of a Lewis acid, preferably of BF 3 , AlCl 3 or / and ZnI 2 , to be performed.

Damit wird es erstmals überraschenderweise möglich, die verschiedensten Olefine individuell auf unterschiedliche Eigenschaften aufgrund geringer Variation der Katalysebedingungen oder/und der Katalysatoren maßzuschneidern, da das erfindungsgemäße Verfahren zur Herstellung von Olefinen eine unerwartet hohe Toleranz gegenüber funktionellen Gruppen aufweist.In order to It will be the first time, surprisingly possible, the most diverse olefins individually to different properties due to small variation of the catalytic conditions or / and the Tailor catalysts, since the inventive method for the production of olefins an unexpectedly high tolerance to functional Has groups.

Beispiele:Examples:

1) Herstellung der Komplexverbindung1) Preparation of the complex compound

Allgemeine Arbeitsvorschrift:General procedure:

1 mmol (PPh3)2Cl2Ru(=CHPh) wurden in 20 ml Toluol gelöst und mit einer Lösung von 2.2 equiv des entsprechenden Imidazolin-2-ylidens in 5 ml Toluol versetzt. Die Reaktionslösung wurde 45 min bei Raumtemperatur RT gerührt, anschließend auf ca. 2 ml eingeengt, und das Rohprodukt wurde mit 25 ml Pentan ausgefällt Das Rohprodukt wurde mehrmals in 2 ml Toluol aufgenommen und mit 25 ml Pentan ausgefällt. Der Rückstand wurde mit Toluol extrahiert, die Lösung zur Trockene eingeengt, mit Pentan zweimal gewaschen und mehrere Stunden im Hochvakuum getrocknet.1 mmol (PPh 3 ) 2 Cl 2 Ru (= CHPh) were dissolved in 20 ml of toluene and treated with a solution of 2.2 equiv of the corresponding imidazolin-2-ylidene in 5 ml of toluene. The reaction solution was stirred for 45 min at room temperature RT, then concentrated to about 2 ml, and the crude product was precipitated with 25 ml of pentane. The crude product was taken up several times in 2 ml of toluene and precipitated with 25 ml of pentane. The residue was extracted with toluene, the solution was concentrated to dryness, washed twice with pentane and dried under high vacuum for several hours.

Zur Charakterisierung werden größtenteils die Daten von Tieftemperatur-NMR-Spektren angegeben, da die Spektren bei Raumtemperatur aufgrund dynamischer Effekte teilweise nicht die gesamte Information enthalten.to Characterization largely become the data from low temperature NMR spectra given since the spectra at room temperature due to dynamic Effects partially do not contain all the information.

Nach der angegebenen allgemeinen Arbeitsvorschrift werden folgende Verbindungen dargestelltTo the specified general working instructions are the following compounds shown

1a) Benzyliden-dichloro-bis(1,3-diisopropylimidazolin-2-yliden)-ruthenium – Komplexverbindung 1: (nicht gemäß Erfindung)1a) Benzylidene-dichloro-bis (1,3-diisopropylimidazolin-2-ylidene) ruthenium complex compound 1: (not according to invention)

  • Ausbeute: 487 mg (0.86 mmol = 86% der Theorie)Yield: 487 mg (0.86 mmol = 86% of theory)
  • Elementaranalyse EA für C25H38Cl2N4Ru (566.58): gefunden C 53.21 H 6.83 N 9.94; berechnet C 53.00 H 6.76 N 9.89.Elemental analysis EA for C 25 H 38 Cl 2 N 4 Ru (566.58): found C 53.21 H 6.83 N 9.94; calculated C 53.00 H 6.76 N 9.89.
  • 1H-NMR (CD2Cl2/200 K): δ 20.33 (1H, s, Ru=CH), 8.25 (2H, d, 3JHH = 7.6 Hz, o-H von C5H5), 7.63 (1H, t, 3JHH = 7.6 Hz, p-H von C6H5), 7.34 (2H, t, m-H von C6H5, 3JHH = 7.6 Hz), 7.15 (2H, br, NCH), 7.03 (2H, br, NCH), 5.97 (2H, spt, 3JHH = 6.4 Hz, NCHMe2), 3.73 (2H, spt, 3JHH 6.4 Hz, NCHMe2), 1.64 (12H, d, 3JHH = 6.4 Hz, NCHMe2), 1.11 (6H, d, 3JHH = 6.4 Hz, NCHMe2), 0.75 (6H, d, 3JHH = 6.4 Hz, NCHMe2). 1 H-NMR (CD 2 Cl 2 / 200K): δ 20:33 (1H, s, Ru = CH), 8.25 (2H, d, 3 J HH = 7.6 Hz, OH of C 5 H 5), 7.63 (1 H , t, 3 J HH = 7.6 Hz, pH of C 6 H 5 ), 7.34 (2H, t, mH of C 6 H 5 , 3 J HH = 7.6 Hz), 7.15 (2H, br, NCH), 7.03 ( 2H, br, NCH), 5.97 (2H, spt, 3 J HH = 6.4 Hz, NCHMe 2 ), 3.73 (2H, spt, 3 J HH 6.4 Hz, NCHMe 2 ), 1.64 (12H, d, 3 J HH = 6.4 Hz, NCHMe 2 ), 1.11 (6H, d, 3 J HH = 6.4 Hz, NCHMe 2 ), 0.75 (6H, d, 3 J HH = 6.4 Hz, NCHMe 2 ).
  • 13C-NMR (CD2Cl2/200 K): 3295.6 (Ru=CH), 183.5 (NCN), 151.6 (ipso-C von C6H5), 129.5, 128.6 und 128.1 (o-C, m-C und p-C von C6H5), 118.1 und 117.2 (NCH), 52.1 und 50.1 (NCHMe2), 24.5, 23.8, 23.8 und 22.4 (NCHMe2). 13 C-NMR (CD 2 Cl 2 / 200K): 3295.6 (Ru = CH), 183.5 (NCN), 151.6 (ipso-C of C 6 H 5), 129.5, 128.6 and 128.1 (oC, mC and pC of C 6 H 5 ), 118.1 and 117.2 (NCH), 52.1 and 50.1 (NCHMe 2 ), 24.5, 23.8, 23.8 and 22.4 (NCHMe 2 ).

1b) Benzyliden-dichloro-bis(1,3-di-((R)-1-phenylethyl)imidazolin-2-yliden)-ruthenium – Komplexverbindung 2: (nicht gemäß Erfindung)1b) Benzylidene-dichloro-bis (1,3-di - ((R) -1-phenylethyl) imidazolin-2-ylidene) ruthenium complex compound 2: (not according to invention)

  • Ausbeute: 676 mg (0.83 mmol = 83% d. Th.)Yield: 676 mg (0.83 mmol = 83% of theory)
  • EA für C45H46Cl2N4Ru (814.86): gef. C 66.48 H 5.90 N 6.73; ber. C 66.33 H 5.69 N 6.88.EA for C 45 H 46 Cl 2 N 4 Ru (814.86): gef. C 66.48 H 5.90 N 6.73; C 66.33 H 5.69 N 6.88.
  • 1H-NMR (CD2Cl2/200 K): δ 20.26 (1H, s, Ru=CH), 8.13 (2H, br, o-H C6H5), 7.78-6.67 (29H, davon 2m-H und 1p-H von C6H5, 20H von NCHMePh, 2H von NCHMePh und 4H von NCH), 4.91 (2H, m, NCHMePh), 1.84 (3H, d, 3JHH = 6.6 Hz, NCHMePh), 1.81 (3H, d, 3JHH = 6.6 Hz, NCHMePh), 1.51 (3H, d, 3JHH = 6.6 Hz, NCHMePh), 1.21 (3H, d, 3JHH = 6.6 Hz, NCHMePh). 1 H-NMR (CD 2 Cl 2 / 200K): δ 20:26 (1H, s, Ru = CH), 8.13 (2H, br, OH C 6 H 5), 7.78-6.67 (29H, 2m-H thereof and 1p-H of C 6 H 5, 20H of NCHMePh, 2H of NCHMePh and 4H from NCH), 4.91 (2H, m, NCHMePh), 1.84 (3H, d, 3 J HH = 6.6 Hz, NCHMePh), 1.81 (3H , d, 3 J HH = 6.6 Hz, NCHMePh), 1.51 (3H, d, 3 J HH = 6.6 Hz, NCHMePh), 1.21 (3H, d, 3 J HH = 6.6 Hz, NCHMePh).
  • 13C-NMR (CD2Cl2/200 K): δ 294.7 (Ru=CH), 186.0 und 185.6 (NCN), 151.2 (ipso-C von C6H5), 141.2, 140.3, 140.1 und 139.9 (ipso-C von NCHMePh), 133.1-125.9 (o-C, m-C, p-C von C6H5 und NCHMePh), 120.5, 119.9, 119.2 und 118.8 (NCH), 57.6, 57.4, 56.7 und 56.1 (NCHMePh), 22.2, 20.6, 20.4 und 20.3 (NCHMePh). 13 C-NMR (CD 2 Cl 2 / 200K): δ 294.7 (Ru = CH), 186.0 and 185.6 (NCN), 151.2 (ipso-C of C 6 H 5), 141.2, 140.3, 140.1 and 139.9 (ipso -C of NCHMePh), 133.1-125.9 (oC, mC, pC of C 6 H 5 and NCHMePh), 120.5, 119.9, 119.2 and 118.8 (NCH), 57.6, 57.4, 56.7 and 56.1 (NCHMePh), 22.2, 20.6, 20.4 and 20.3 (NCHMePh).

1c) Benzyliden-dichloro-bis(1,3-di-((R)-1'-naphtylethyl)imidazolin-2-yliden)-ruthenium – Komplexverbindung 3: (nicht gemäß Erfindung)1c) Benzylidene-dichloro-bis (1,3-di - ((R) -1'-naphthylethyl) imidazolin-2-ylidene) ruthenium complex compound 3: (not according to invention)

  • Ausbeute: 792 mg (0.78 mmol = 78% d. Th.)Yield: 792 mg (0.78 mmol = 78% of theory)
  • EA für C61H54Cl2N4Ru (1015.1): gef. C 72.34 H 5.46 N 5.45; ber. C 72.18 H 5.36 N 5.52.EA for C 61 H 54 Cl 2 N 4 Ru (1015.1): gef. C 72.34 H 5.46 N 5.45; C 72.18 H 5.36 N 5.52.
  • 1H-NMR (CD2Cl2/260 K): δ 20.90 (1H, s, Ru=CH), 8.99 (2H, br, o-H von C6H5), 8.2-5.6 (39H, davon 2m-H und 1p-H von C6H5, 28H von NCHMeNaph, 4H von NCH und 4H von NCHMeNaph), 2.5-0.8 (12H, m, NCHMeNaph). 1 H-NMR (CD 2 Cl 2 / 260K): δ 20.90 (1H, s, Ru = CH), 8.99 (2H, br, OH of C 6 H 5), 8.2-5.6 (39H, thereof 2m-H and 1p-H of C 6 H 5 , 28H of NCHMeNaph, 4H of NCH and 4H of NCHMeNaph), 2.5-0.8 (12H, m, NCHMeNaph).
  • 13C-NMR (CD2Cl2/260 K): δ 299.9 (Ru=CH), 187.2 und 184.7 (NCN), 152.0 (ipso-C von C6H5), 136.0-124.0 (o-C, m-C, p-C von C6H5 und NCHMeNaph), 121.7, 121.0, 119.9 und 118.9 (NCH), 56.7, 56.1, 55.0 und 54.7 (NCHMeNaph), 24.7, 24.3, 21.0 und 20.0 (NCHMeNaph). 13 C-NMR (CD 2 Cl 2 / 260K): δ 299.9 (Ru = CH), 187.2 and 184.7 (NCN), 152.0 (ipso-C of C 6 H 5), 136.0-124.0 (oC, mC, pC of C 6 H 5 and NCHMeNaph), 121.7, 121.0, 119.9 and 118.9 (NCH), 56.7, 56.1, 55.0 and 54.7 (NCHMeNaph), 24.7, 24.3, 21.0 and 20.0 (NCHMeNaph).

Für die folgenden Komplexe sind geringfügige Abweichungen von der allgemeinen Arbeitsvorschrift notwendig:For the following Complexes are minor Deviations from the general working instructions necessary:

1d) (4-Chlorbenzyliden)-dichloro-bis(1,3-diisopropylimidazolin-2-yliden)-ruthenium – Komplexverbindung 4: (nicht gemäß Erfindung)1d) (4-chlorobenzylidene) dichloro-bis (1,3-diisopropylimidazolin-2-ylidene) ruthenium complex 4: (not according to invention)

Als Edukt wurde 1 mmol (PPh3)2Cl2Ru[=CH(p-C6H4Cl)] eingesetzt. Die weitere Vorgehensweise entsprach der allgemeinen Arbeitsvorschrift.

  • Ausbeute: 535 mg (0.89 mmol = 89% d. Th.)
  • EA für C24H38Cl3N4Ru (601.03): gef. C 48.13 H 6.33 N 9.24; ber. C 47.96 H 6.37 N 9.32.
  • 1H-NMR (CD2Cl2/200 K): δ 20.33 (1H, s, Ru=CH), 8.25 (214, d, 3JHH = 7.6 Hz, o-H von C6H4Cl), 7.63 (1H, t, 3JHH = 7.6 Hz, m-H von C6H4Cl), 7.15 (2H, br, NCH), 7.03 (2H, br, NCH), 5.97 (2H, spt, 3JHH = 6.4 Hz, NCHMe2), 3.73 (2H, spt, 3JHH = 6.4 Hz, NCHMe2), 1.64 (12H, d, 3JHH = 6.4 Hz, NCHMe2), 1.11 (6H, d, 3JHH = 6.4 Hz, NCHMe2), 0.75 (6H, d, 3JHH = 6.4 Hz, NCHMe2).
  • 13C-NMR (CD2Cl2/200 K): δ 295.6 (Ru=CH), 183.5 (NCN), 151.6 (ipso-C von C6H4Cl), 134.3 (p-C von C6H4Cl), 128.6 und 128.1 (o-C und m-C von C6H4Cl), 118.1 und 117.2 (NCH), 52.1 und 50,1 (NCHMe2), 24.5, 23.8, 23.8 und 22.4 (NCHMe2).
The starting material used was 1 mmol of (PPh 3 ) 2 Cl 2 Ru [= CH (pC 6 H 4 Cl)]. The further procedure corresponded to the general working instructions.
  • Yield: 535 mg (0.89 mmol = 89% of theory)
  • EA for C 24 H 38 Cl 3 N 4 Ru (601.03): gef. C 48.13 H 6.33 N 9.24; C 47.96 H 6.37 N 9.32.
  • 1 H-NMR (CD 2 Cl 2 / 200K): δ 20:33 (1H, s, Ru = CH), 8.25 (214, d, 3 J HH = 7.6 Hz, OH of C 6 H 4 Cl), 7.63 ( 1H, t, 3 J HH = 7.6 Hz, mH of C 6 H 4 Cl), 7.15 (2H, br, NCH), 7.03 (2H, br, NCH), 5.97 (2H, spt, 3 J HH = 6.4 Hz , NCHMe 2 ), 3.73 (2H, spt, 3 J HH = 6.4 Hz, NCHMe 2 ), 1.64 (12H, d, 3 J HH = 6.4 Hz, NCHMe 2 ), 1.11 (6H, d, 3 J HH = 6.4 Hz, NCHMe 2 ), 0.75 (6H, d, 3 J HH = 6.4 Hz, NCHMe 2 ).
  • 13 C-NMR (CD 2 Cl 2 / 200K): δ 295.6 (Ru = CH), 183.5 (NCN), 151.6 (ipso-C of C 6 H 4 Cl), 134.3 (pC of C 6 H 4 Cl) , 128.6 and 128.1 (oC and mC of C 6 H 4 Cl), 118.1 and 117.2 (NCH), 52.1 and 50.1 (NCHMe 2 ), 24.5, 23.8, 23.8 and 22.4 (NCHMe 2 ).

1e) Benzyliden-dichloro-bis(1,3-dicyclohexylimidazolin-2-yliden)-ruthenium – Komplexverbindung 5: (nicht gemäß Erfindung)1e) Benzylidene-dichloro-bis (1,3-dicyclohexylimidazolin-2-ylidene) ruthenium complex compound 5: (not according to invention)

1 mmol (PPh3)2Cl2Ru(=CHPh) wurden in 25 ml Toluol gelöst und mit einer Lösung, von 2.2 equiv. 1,3-Dicyclohexylimidazolin-2-yliden in 5 ml Toluol versetzt. Die Reaktionslösung wurde 45 min bei RT gerührt und anschließend vom Lösungsmittel befreit. Anders als bei der allgemeinen Arbeitsvorschrift wurde das Rohprodukt durch Flashchromatographie gereinigt

  • Ausbeute: 305 mg (0.42 mmol = 42% d. Th.)
  • EA für C37H54Cl2N4Ru (726.84): gef. C 61.23 H 7.56 N 7.87; ber. C 61.14 H 7.49 N 7.71.
  • 1H-NMR (CD2Cl2/298 K): 320.45 (1H, s, Ru=CH), 8.31 (2H, d, 3JHH = 7.6 Hz, o-H- von C6H5), 7.63 (1H, t, 3JHH = 7.6 Hz, p-H- von C6H5), 7.34 (2H, t, 3JHH = 7.6 Hz, m-H- von C6H5), 7.14 (2H, br, NCH), 7.00 (2H, br, NCH), 6.06 (2H, br, CH von NC6H11), 3.82 (2H, br, CH von NC6H11), 1.64 (12H, br, CH2 von NC6H11), 0.93 (12H, br, CH2 von NC6H11).
  • 13C-NMR (CD2Cl2/298 K): δ 299.4 (Ru=CH), 182.9 (NCN), 152.0 (ipso-C von C6H5), 131.1, 129.8 und 129.1 (o-C, m-C und p-C von C6H5), 118.3 und 117.8 (br, NCH), 59.6 und 57.5 (br, CH von NC6H11), 35.7, 26.9. und 25.6 (br, CH2 von NC6H11).
1 mmol (PPh 3 ) 2 Cl 2 Ru (= CHPh) were dissolved in 25 ml of toluene and washed with a solution of 2.2 equiv. Added 1,3-dicyclohexylimidazolin-2-ylidene in 5 ml of toluene. The reaction solution was stirred at RT for 45 min and then freed from the solvent. Unlike the general procedure, the crude product was purified by flash chromatography
  • Yield: 305 mg (0.42 mmol = 42% of theory)
  • EA for C 37 H 54 Cl 2 N 4 Ru (726.84): gef. C 61.23 H 7.56 N 7.87; C 61.14 H 7.49 N 7.71.
  • 1 H-NMR (CD 2 Cl 2/298 K): 320.45 (1H, s, Ru = CH), 8.31 (2H, d, 3 J HH = 7.6 Hz, OH of C 6 H 5), 7.63 (1 H , t, 3 J HH = 7.6 Hz, pH of C 6 H 5 ), 7.34 (2H, t, 3 J HH = 7.6 Hz, mH of C 6 H 5 ), 7.14 (2H, br, NCH), 7.00 (2H, br, NCH), 6.06 (2H, br, CH of NC 6 H 11 ), 3.82 (2H, br, CH of NC 6 H 11 ), 1.64 (12H, br, CH 2 of NC 6 H 11 ), 0.93 (12H, br, CH 2 of NC 6 H 11 ).
  • 13 C-NMR (CD 2 Cl 2/298 K): δ 299.4 (Ru = CH), 182.9 (NCN), 152.0 (ipso-C of C 6 H 5), 131.1, 129.8 and 129.1 (oC, mC and pC of C 6 H 5 ), 118.3 and 117.8 (br, NCH), 59.6 and 57.5 (br, CH of NC 6 H 11 ), 35.7, 26.9. and 25.6 (br, CH 2 of NC 6 H 11 ).

1f) Benzyliden-dichloro-(1,3-di-tert.-butylimidazolin-2-yliden)-(triphenylphosphin)-ruthenium – Komplexverbindung 6:1f) Benzylidene-dichloro (1,3-di-tert-butylimidazolin-2-ylidene) - (triphenylphosphine) ruthenium complex compound 6:

1 mmol (PPh3)2Cl2Ru(=CHPh) wurden in 20 ml Toluol gelöst und mit einer Lösung von 1.1 equiv. 1,3-Di-tert.-butylimidazolin-2-yliden in 5 ml Toluol versetzt. Die Reaktionslösung wurde 30 min bei RT gerührt, anschließend auf ca. 2 ml eingeengt, und das Rohprodukt wurde mit 25 ml Pentan ausgefällt. Die Weitere Aufarbeitung erfolgte gemäß der allgemeinen Arbeitsvorschrift.

  • Ausbeute: 493 mg (0.70 mmol = 70% d. Th.)
  • EA für C36H41Cl2N2P1Ru (704.69): gef. C 61.12 H 5.55 N 3.62 P 4.59 ber. C 61.36 H 5.86 N 3.98 P 4.38.
  • 1H-NMR (CD2Cl2/200 K): δ 20.70 (1H, s, Ru=CH), 8.03 (2H, d, 3JHH = 7.6 Hz, o-H von C6H5), 7.50-6.95 (20H, davon 2m-H und 1p-H von C6H5, 15H von PPh3 und 2H von NCH), 1.86 (9H, s, NCMe3), 1.45 (9H, s, NCMe3).
  • 13C-NMR (CD2Cl2/200 K): δ 307.4 (br, Ru=CH), 178.3 (d, JPC = 86 Hz, NCN), 151.5 (d, JPC = 4.5 Hz, ipso-C von C6H5), 135.0 (m, o-C von PPh3), 131.9 (m, ipso-C von PPh3), 130.2 (s, p-C von PPh3), 129.5, 128.6 und 128.1 (s, o-C, m-C und p-C von C6H5), 128.0 (m, m-C von PPh3), 117.7 und 117.6 (NCH), 58.7 und 58.5 (NCMe3), 30.0 und 29.5 (NCMe3).
  • 31P-NMR (CD2Cl2/200 K): δ 40.7 (s, PPh3).
1 mmol (PPh 3 ) 2 Cl 2 Ru (= CHPh) were dissolved in 20 ml of toluene and treated with a solution of 1.1 equiv. Added 1,3-di-tert-butylimidazolin-2-ylidene in 5 ml of toluene. The reaction solution was stirred for 30 min at RT, then concentrated to about 2 ml, and the crude product was precipitated with 25 ml of pentane. The further work-up was carried out according to the general working instructions.
  • Yield: 493 mg (0.70 mmol = 70% of theory)
  • EA for C 36 H 41 Cl 2 N 2 P 1 Ru (704.69): gef. C 61.12 H 5.55 N 3.62 P 4.59 Superv. C 61.36 H 5.86 N 3.98 P 4.38.
  • 1 H-NMR (CD 2 Cl 2 / 200K): δ 20.70 (1H, s, Ru = CH), 8:03 (2H, d, 3 J HH = 7.6 Hz, OH of C 6 H 5), 7.50-6.95 (20H, of which 2m-H and 1p-H of C 6 H 5 , 15H of PPh 3 and 2H of NCH), 1.86 (9H, s, NCMe 3 ), 1.45 (9H, s, NCMe 3 ).
  • 13 C-NMR (CD 2 Cl 2 / 200K): δ 307.4 (br, Ru = CH), 178.3 (d, J PC = 86 Hz, NCN), 151.5 (d, J PC = 4.5 Hz, ipso-C of C 6 H 5 ), 135.0 (m, oC of PPh 3 ), 131.9 (m, ipso-C of PPh 3 ), 130.2 (s, pC of PPh 3 ), 129.5, 128.6 and 128.1 (s, oC, mC and pC of C 6 H 5 ), 128.0 (m, mC of PPh 3 ), 117.7 and 117.6 (NCH), 58.7 and 58.5 (NCMe 3 ), 30.0 and 29.5 (NCMe 3 ).
  • 31 P NMR (CD 2 Cl 2 / 200K): δ 40.7 (s, PPh 3).

2) Anwendung der Komplexverbindung bei der Olefin-Metathese2) Use of the complex compound in olefin metathesis

Die im folgenden aufgeführten Beispiele demonstrieren das Potential der erfindungsgemäßen Komplexverbindungen in der Olefin-Metathese. Der Vorteil dieser erfindungsgemäßen Komplexverbindungen verglichen mit phosphanhaltigen Komplexen liegt in der gezielten und kostengünstigen Variation der Reste R an den Stickstoffatomen der N-heterozyklischen Carbenliganden. Durch diese Maßschneiderung der erfindungsgemäßen Katalysatoren bezogen auf individuelle Eigenschaften der zu metathesierenden Olefine können Aktivität wie Selektivität der Reaktion gesteuert werden.The listed below Examples demonstrate the potential of the complex compounds of the invention in olefin metathesis. The advantage of these complex compounds according to the invention Compared with phosphine-containing complexes lies in the targeted and cost-effective Variation of the radicals R at the nitrogen atoms of the N-heterocyclic Carbene ligands. By this tailoring the catalysts of the invention based on individual properties of the olefins to be metathesized can activity like selectivity the reaction can be controlled.

Die Reaktion und den Komplexen 1 bis 5 ist nicht gemäß Erfindung.The Reaction and complexes 1 to 5 is not according to the invention.

2a) Ringöffnende Metathese-Polymerisation (ROMP):2a) Ring-opening metathesis polymerization (ROMP):

Als Beispiele dienen Norbornen, Cycloocten und funktionalisierte Norbornenderivate.When Examples are norbornene, cyclooctene and functionalized norbornene derivatives.

Figure 00130001
Figure 00130001

Typischer Reaktionsansatz für die Polymerisation von Cycloocten (bzw. Norbornen):Typical reaction mixture for the polymerization of cyclooctene (or norbornene):

In eine Lösung von 3.6 mg (6.3 μmol) 1 in 0.5 ml Methylenchlorid wurden 410 μl (3.13 mmol) Cycloocten gegeben. Nach ca. 10 min hatte sich ein hochviskoses Gel gebildet, das nicht mehr gerührt werden konnte. Es wurde 1 ml Methylenchlorid zugesetzt. Diese Prozedur wurde immer dann wiederholt, wenn keine Rührerleistung mehr vorhanden war (insgesamt 3 ml Methylenchlorid). Nach 1 h wurden 5 ml Methylenchlorid zugegeben, dem geringe Mengen von tert-Butylether und 2,6-Ditert-butyl-4-methylphenol zugesetzt wurden. Nach weiteren 10 min wurde die Lösung in einen hohen Überschuß von Methanol langsam eingetropft, filtriert und im Hochvakuum über mehrere Stunden getrocknet.
Ausbeute: 291 mg (2.64 mmol = 84.3% d. Th.) Tabelle 1. Polymerisation von Norbornen und Cycloocten Beispiel Komplex Monomer Verhältnis[Monomer]/[Kat.] Reaktionszeit t Ausbeute 2.1a 1 Norbornen 100:1 1 min 91% 2.1b 5 Norbornen 100:1 1 min 92% 2.1c 1 Cycloocten 500:1 1 h 84% 2.1d 1 Cycloocten 500:1 2 h 97% 2.1e 5 Cycloocten 500:1 1 h 87% To a solution of 3.6 mg (6.3 μmol) of 1 in 0.5 ml of methylene chloride was added 410 μl (3.13 mmol) of cyclooctene. After about 10 minutes, a highly viscous gel had formed, which could no longer be stirred. 1 ml of methylene chloride was added. This procedure was repeated whenever there was no more stirrer power (total 3 ml of methylene chloride). After 1 h, 5 ml of methylene chloride was added to which small amounts of tert-butyl ether and 2,6-di-tert-butyl-4-methylphenol were added. After a further 10 minutes, the solution was slowly added dropwise into a large excess of methanol, filtered and dried under high vacuum for several hours.
Yield: 291 mg (2.64 mmol = 84.3% of theory) Table 1. Polymerization of norbornene and cyclooctene example complex monomer Ratio of [monomer] / [Cat.] Reaction time t yield 2.1a 1 norbornene 100: 1 1 min 91% 2.1b 5 norbornene 100: 1 1 min 92% 2.1c 1 cyclooctene 500: 1 1 h 84% 2.1d 1 cyclooctene 500: 1 2 h 97% 2.1e 5 cyclooctene 500: 1 1 h 87%

Typischer Reaktionsansatz für die Polymerisation von funktionalisierten Norbornenderivaten:Typical reaction mixture for the polymerization of functionalized norbornene derivatives:

Die Formel VII veranschaulicht das Grundgerüst der in Tabelle 2 eingesetzten Norbornenderivate.The Formula VII illustrates the backbone of those used in Table 2 Norbornene derivatives.

Figure 00140001
Figure 00140001

Zu einer Lösung von 3.6 mg (6.3 μmol) 1 in 0.2 ml Methylenchlorid wurden 0.3 ml einer Lösung von 432 mg (3.13 mmol) 5-Carbonsäure-2-norbornen (Formel VII) mit R = CO2H) in Methylenchlorid gegeben. Nach ca. 10 min hatte sich ein hochviskoses Gel gebildet, das nicht mehr gerührt werden konnte. Es wurden weitere 0.5 ml Methylenchlorid zugesetzt. Diese Prozedur wurde immer dann wiederholt, wenn keine Rührerleistung mehr vorhanden war. Nach 1 h wurden 5 ml Methylenchlorid zugegeben, dem geringe Mengen von tert-Butylether und 2,6-Di-tert-butyl-4-methylphenol zugesetzt waren. Nach weiteren 10 min wurde die Lösung in einen. hohen Überschuß von Methanol langsam eingetropft, filtriert und im Hochvakuum über mehrere Stunden getrocknet.
Ausbeute: 423 mg (3.06 mmol = 98.1% d. Th.)To a solution of 3.6 mg (6.3 μmol) of 1 in 0.2 ml of methylene chloride was added 0.3 ml of a solution of 432 mg (3.13 mmol) of 5-carboxylic acid 2-norbornene (formula VII) with R = CO 2 H) in methylene chloride. After about 10 minutes, a highly viscous gel had formed, which could no longer be stirred. An additional 0.5 ml of methylene chloride was added. This procedure was repeated whenever there was no more stirring power. After 1 h, 5 ml of methylene chloride were added to which small amounts of tert-butyl ether and 2,6-di-tert-butyl-4-methylphenol were added. After a further 10 minutes, the solution became one. dripped slowly high excess of methanol, filtered and dried under high vacuum for several hours.
Yield: 423 mg (3.06 mmol = 98.1% of theory)

Die Reaktionen bei 50°C erfolgten in analoger Weise in Dichlorethan statt in Methylenchlorid. Tabelle 2. Polymerisation funktionalisierter Norbornenderivate Beispiel Komplex Rest R in Formel VII T [°C] Reaktionszeit t Ausbeute 2.1f 1 O2CCH3 25 30 min 99% 2.1g 1 CH2OH 25 2 h 15% 2.1h 1 CH2OH 50 2 h 18% 2.1i 1 CHO 25 2 h 36% 2.1k 1 CHO 50 2 h 52% 2.1l 1 COCH3 25 2 h 42% 2.1m 1 COCH3 50 2 h 67% 2.1n 1 CO2H 25 2 h 98% The reactions at 50 ° C were carried out in an analogous manner in dichloroethane instead of methylene chloride. Table 2. Polymerization of functionalized norbornene derivatives example complex R in formula VII T [° C] Reaction time t yield 2.1f 1 O 2 CCH 3 25 30 min 99% 2.1g 1 CH 2 OH 25 2 h 15% 2.1h 1 CH 2 OH 50 2 h 18% 2.1i 1 CHO 25 2 h 36% 2.1K 1 CHO 50 2 h 52% 2.1l 1 COCH 3 25 2 h 42% 2.1m 1 COCH 3 50 2 h 67% 2.1n 1 CO 2 H 25 2 h 98%

Die Polymerisation von Norbornen erfolgte dabei in Sekundenfrist. Bei der Cyclooctenpolymerisation wurden innerhalb einer Stunde nahezu quantitative Umsätze erhalten (Tabelle 1). Unterschiede bezüglich der Aktivität sind durch Einsatz verschiedener Komplexe unter verdünnten Bedingungen nachweisbar und zeigen die Abhängigkeit der Aktivität vom Substitutionsmuster der eingesetzten Garbenliganden. Die hohe Stabilität und Toleranz gegenüber funktionellen Gruppen wird durch die Polymerisation funktionalisierter Norbornenderivate mit Ester, Alkohol, Aldehyd, Keton oder/und Carbonsäure demonstriert (Tabelle 2). Dabei konnten Monomere der allgemeinen Formel VII mit R = CH2OH, CHO und CO2H erstmals polymerisiert werden. 2.2) Ringschluß-Metathese (RCM) von 1,7-Octadien:

Figure 00150001
The polymerization of norbornene took place within seconds. In cyclooctene polymerization, nearly quantitative conversions were obtained within one hour (Table 1). Differences in activity can be detected by the use of different complexes under dilute conditions and show the dependence of the activity on the substitution pattern of the garlic ligands used. The high stability and tolerance to functional groups is demonstrated by the polymerization of functionalized norbornene derivatives with ester, alcohol, aldehyde, ketone and / or carboxylic acid (Table 2). In this case, monomers of the general formula VII with R = CH 2 OH, CHO and CO 2 H were first polymerized. 2.2) Ring-closing metathesis (RCM) of 1,7-octadiene:
Figure 00150001

Typischer Reaktionsansatz für RCM von 1,7-Octadien:Typical reaction for RCM of 1,7-octadiene:

Eine Lösung von 3.6 mg (6.3 μmol) 1 in 2 ml Dichlorethan wurde mit 46 μl (0.31 mmol) 1,7-Octadien versetzt, und der Reaktionsansatz wurde in ein 60°C warmes Ölbad gegeben. Nach 1 h wurde das Reaktionsgemisch GC/MS-analytisch untersucht. Tabelle 3. RCM von 1,7-Octadien (Octadien/Katalysator = 50:1) Beispiel Komplex Lösungsmittel T [°C] Reaktionszeit t Ausbeute 2.2a 1 Methylenchlorid 25 5.5 h 51% 2.2b 1 Methylenchlorid 25 24 h 70% 2.2c 1 Dichlorethan 60 1 h 99% 2.2d 2 Dichlorethan 60 1 h 99% 2.2e 3 Dichlorethan 60 1 h 99% 2.2f 5 Dichlorethan 60 1 h 99% To a solution of 3.6 mg (6.3 μmol) of 1 in 2 ml of dichloroethane was added 46 μl (0.31 mmol) of 1,7-octadiene, and the reaction was added to a 60 ° C oil bath. After 1 h, the reaction mixture was analyzed by GC / MS analysis. Table 3. RCM of 1,7-octadiene (octadiene / catalyst = 50: 1) example complex solvent T [° C] Reaction time t yield 2.2a 1 methylene chloride 25 5.5 h 51% 2.2b 1 methylene chloride 25 24 hours 70% 2.2c 1 dichloroethane 60 1 h 99% 2.2d 2 dichloroethane 60 1 h 99% 2.2e 3 dichloroethane 60 1 h 99% 2.2f 5 dichloroethane 60 1 h 99%

Das Potential in der Ringschluß-Metathese wurde durch die Reaktion von 1,7-Octadien zu Cyclohexen unter Freisetzung von Ethylen veranschaulicht (Tabelle 3).The Potential in ring-closing metathesis was due to the reaction of 1,7-octadiene to cyclohexene to release ethylene (Table 3).

Mit 1 wurde nach 5.5 h eine Ausbeute von 51% erzielt, bei 60°C wurden mit allen eingesetzten erfindungsgemäßen Komplexverbindungen sogar quantitative Umsätze erzieltWith 1, a yield of 51% was achieved after 5.5 h, at 60 ° C were even with all complex compounds of the invention used quantitative sales achieved

2.3) Metathese acyclischer Olefine2.3) Metathesis of acyclic olefins

A) Metathese von 1-Octen:

Figure 00160001
A) Metathesis of 1-octene:
Figure 00160001

Figure 00170001
Figure 00170001

Typischer Reaktionsansatz der Metathese von 1-Octen:Typical reaction of metathesis from 1-octene:

Eine Lösung von 3.6 mg (6.3 μmol) 1 in 2 ml Dichlorethan wurde mit 49 μl (0.31 mmol) 1-Octen versetzt, und der Reaktionsansatz wurde in ein 60°C heißes Ölbad gegeben. Nach 3 h wurde das Reaktionsgemisch GC/MS-analytisch untersucht Tabelle 4. Homo-Metathese von 1-Octen (Octen/Katalysator = 50:1) Beispiel Komplex T [°C] Reaktionszeit t Umsatz von 1-Octen Selektivitäta 2.3a 2 60 1 h 31% 98% 2.3b 2 60 2 h 58% 97% 2.3c 1 60 1 h 83% 73% 2.3d 1 60 3 h 97% 63%

  • a Die Selektivität gibt den Anteil an 7-Tetradecen gegenüber anderen metathetischen Produkten an
B) Metathese von Methyloleat:
Figure 00170002
A solution of 3.6 mg (6.3 μmol) of 1 in 2 ml of dichloroethane was added with 49 ul (0.31 mmol) of 1-octene, and the reaction was poured into a 60 ° C oil bath. After 3 h, the reaction mixture was analyzed by GC / MS analysis. TABLE 4 Homo-metathesis of 1-octene (octene / catalyst = 50: 1) example complex T [° C] Reaction time t Sales of 1-octene Selectivity a 2.3a 2 60 1 h 31% 98% 2.3b 2 60 2 h 58% 97% 2.3c 1 60 1 h 83% 73% 2.3d 1 60 3 h 97% 63%
  • a The selectivity indicates the proportion of 7-tetradecene compared to other metathetic products
B) Metathesis of methyl oleate:
Figure 00170002

Typischer Reaktionsansatz für die Metathese von Methyloleat:Typical reaction approach for metathesis of methyl oleate:

Eine Lösung von 3.6 mg (6.3 μmol) 1 in 0.5 ml Dichlorethan wurde mit 1.06 ml (3.13 mmol) Methyloleat versetzt, und der Reaktionsansatz wurde für 15 h in ein 60°C warmes Ölbad gegeben. Die GC/MS-Analyse ergab das in der Reaktionsgleichung (7) gezeigte Gleichgewicht von Metatheseprodukten.A solution of 3.6 mg (6.3 μmol) 1.06 ml (3.13 mmol) of methyl oleate were added to 1 in 0.5 ml of dichloroethane, and the reaction was for 15 h in a 60 ° C warm oil bath where. GC / MS analysis showed that in the reaction equation (7) shown balance of metathesis products.

Die Metathese von terminalen und innenständigen Olefinen wurde durch die Homo-Metathese von 1-Octen und Methyloleat nachgewiesen. Bei der Metathese von Methyloleat als nativem Rohstoff kann das thermodynamische Gleichgewicht innerhalb von 15 h mit Katalysator 1 bei einem Olefin: Katalysator-Verhältnis von 500:1 nahezu erreicht werden. Bei der Metathese von 1-Octen wurde 7-Tetradecen nicht in allen Fällen als einziges Reaktionsprodukt erhalten. Eine NMR-spektroskopisch nachgewiesene isomerisierung von 1-Octen zu 2-Octen und anschließende Olefin-Metathese ist für diesen Sachverhalt verantwortlich. Durch Homo- und Cross-Metathese von 1-Octen und 2-Octen wurde neben 7-Tetradecen auch als häufigstes Nebenprodukt 6-Tridecen und in geringen Mengen 6-Dodecen, 1-Hepten und 2-Nonen erhalten. Die Produktverteilung ist stark abhängig vom eingesetzten Katalysator. Im Fall von 2 wurde nahezu selektiv 7-Tetradecen erhalten; dagegen lieferte der aktivere Komplex 1 bei hohem Umsatz 7 Tetradecen nur mit einer Selektivität von 63%. Als Nebenprodukt wurde im wesentlichen 6-Tridecen aus der Cross-Metathese von 1-Octen mit 2-Octen erhalten.The Metathesis of terminal and internal olefins was by the homo-metathesis detected by 1-octene and methyl oleate. In the metathesis of Methyloleate as a native raw material can be the thermodynamic equilibrium within 15 h with catalyst 1 at an olefin: catalyst ratio of 500: 1 are almost reached. In the metathesis of 1-octene was 7-tetradecene not in all cases obtained only reaction product. An isomerization detected by NMR spectroscopy from 1-octene to 2-octene followed by olefin metathesis For this Facts responsible. Through homo- and cross-metathesis of 1-octene and 2-octene were also the most common among 7-tetradecene By-product 6-tridecene and in small quantities 6-dodecene, 1-heptene and 2-nonene. The product distribution is highly dependent on used catalyst. In the case of 2, 7-tetradecene became almost selective receive; whereas the more active complex 1 gave a high turnover 7 tetradecene only with a selectivity of 63%. As a by-product became essentially 6-tridecenes obtained from the cross-metathesis of 1-octene with 2-octene.

Claims (13)

Komplexverbindung des Rutheniums der allgemeinen-Strukturformel I,
Figure 00190001
in der X1 und X2 gleich oder verschieden voneinander einen anionischen Liganden bedeuten, in der R1 und R2 gleich oder unabhängig voneinander verschieden sind, aber auch einen Cyclus auf weisen können, in der R1 und R2 für Wasserstoff oder/und für eine Kohlenwasserstoffgruppe stehen, wobei die Kohlenwasserstoffgruppen gleich oder unabhängig voneinander verschieden aus geradkettigen, verzweigten, cyclischen oder/und nicht cyclischen Resten aus der Gruppe von Alkylresten mit 1 bis 50 Kohlenstoffatomen, Alkenylresten mit 1 bis 50 Kohlenstoffatomen, Alkinylresten mit 1 bis 50 Kohlenstoffatomen, Arylresten mit 1 bis 30 Kohlenstoffatomen und Silylresten bestehen, wobei in den Kohlenwasserstoff- oder/und Silylgruppen die Wasserstoffatome teilweise oder gänzlich durch eine Alkyl-, Aryl-, Alkenyl-, Alkinyl-, Metallocenyl-, Halogen-, Nitro-, Nitroso-, Hydroxy-, Alkoxy-, Aryloxy-, Amino-, Amido-, Carboxyl-, Carbonyl-, Thio- oder/und Sulfonylgruppe einfach oder mehrfach, gleich oder unabhängig voneinander verschieden ersetzt sein können, in der der Ligand L1 ein N-heterozyklisches Carben der allgemeinen Formeln II–IV ist und in der der Ligand L2 ein
Figure 00200001
wobei R1', R2', R3' und R4' in den Formeln II, III, IV gleich oder verschieden für Wasserstoff oder/und für Kohlenwasserstoffgruppen stehen, wobei die Kohlenwasserstoffgruppen aus gleichen oder verschiedenen, cyclischen, nicht cyclischen, geradkettigen oder/und verzweigten Resten aus der Gruppe von Alkylresten mit 1 bis 50 Kohlenstoffatomen, Alkenylresten mit 1 bis 50 Kohlenstoffatomen, Alkinylresten mit 1 bis 50 Kohlenstoffatomen und Arylresten mit 1 bis 30 Kohlenstoffatomen bestehen, wobei gegebenenfalls R3' und R4' für Halogen-, Nitro-, Nitroso-, Alkoxy-, Aryloxy-, Amido-, Carboxyl-, Carbonyl-, Thio- oder/und Sulfonylgruppen einfach oder mehrfach, gleich oder unabhängig voneinander verschieden stehen kann.Complex compound of ruthenium of the general structural formula I,
Figure 00190001
in which X 1 and X 2, identical or different, denote an anionic ligand in which R 1 and R 2 are the same or different, but may also have a cycle in which R 1 and R 2 are hydrogen and / or are a hydrocarbon group, wherein the hydrocarbon groups are identical or independently different from straight-chain, branched, cyclic or / and non-cyclic radicals from the group of alkyl radicals having 1 to 50 carbon atoms, alkenyl radicals having 1 to 50 carbon atoms, alkynyl radicals having 1 to 50 carbon atoms, Aryl radicals having from 1 to 30 carbon atoms and silyl radicals, where in the hydrocarbon or / and silyl groups the hydrogen atoms are partially or entirely replaced by an alkyl, aryl, alkenyl, alkynyl, metallocenyl, halogen, nitro, nitroso, Hydroxy, alkoxy, aryloxy, amino, amido, carboxyl, carbonyl, thio or / and sulfonyl group singly or multiply, the same or un may be substituted differently depending on each other, in which the ligand L 1 is an N-heterocyclic carbene of the general formulas II-IV and in which the ligand L 2 a
Figure 00200001
where R 1 ' , R 2' , R 3 ' and R 4' in the formulas II, III, IV are the same or different and denote hydrogen and / or hydrocarbon groups, the hydrocarbon groups being of identical or different, cyclic, noncyclic, straight-chain or / and branched radicals from the group of alkyl radicals having 1 to 50 carbon atoms, alkenyl radicals having 1 to 50 carbon atoms, alkynyl radicals having 1 to 50 carbon atoms and aryl radicals having 1 to 30 carbon atoms, where appropriate R 3 ' and R 4' for halogen , Nitro, nitroso, alkoxy, aryloxy, amido, carboxyl, carbonyl, thio or / and sulfonyl groups may be mono- or polysubstituted, identical or independently different. Komplexverbindung nach Anspruch 1 dadurch gekennzeichnet, daß die anionischen Liganden X1 und X2 gleich oder verschieden Halogenid, Pseudohalogenid, Tetraphenylborat, perhalogeniertes Tetraphenylborat, Tetrahalogenoborat, Hexahalogenophosphat, Hexahalogenoantimonat, Trihalogenomethansulfonat, Alkoxid, Carboxylat, Tetrahalogenoaluminat, Tertracarbonyl-Cobaltat, Hexahalogenoferrat(III), Tetrahalogenoferrat(III) oder/und Tetrahalogenopalladat(II) sind, wobei Halogenid, Pseudohalogenid, Tetraphenylborat, perfluoriertes Tetraphenylborat, Tetrafluoroborat, Hexafluorophosphat, Hexafluoroantimonat, Trifluormethansulfonat, Alkoxid, Carboxylat, Tetrachloroaluminat, Tertracarbonyl-Cobaltat, Hexafluoroferrat(III), Tetrachloroferrat(III) oder/und Tetrachloropalladat(II) bevorzugt sind und wobei unter den Pseudohalogeniden Cyanid, Rhodanid, Cyanat, Isocyanat, Thiocyanat und Isothiocyanat bevorzugt sind.Complex compound according to Claim 1, characterized in that the anionic ligands X 1 and X 2, identical or different, are halide, pseudohalide, tetraphenylborate, perhalogenated tetraphenylborate, tetrahaloborate, hexahalogenophosphate, hexahalogenoantimonate, trihalomethanesulphonate, alkoxide, carboxylate, tetrahaloaluminate, tetracarbonyl cobaltate, hexahalogenoferrate (III) , Tetrahaloferrate (III) or / and tetrahalogenopalladate (II), wherein halide, pseudohalide, tetraphenylborate, perfluorinated tetraphenylborate, tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, trifluoromethanesulfonate, alkoxide, carboxylate, tetrachloroaluminate, tetracarbonyl cobaltate, hexafluoroferrate (III), tetrachloroferrate (III ) and / or tetrachloropalladate (II) are preferred and wherein among the pseudohalides cyanide, rhodanide, cyanate, isocyanate, thiocyanate and isothiocyanate are preferred. Komplexverbindung nach Anspruch 1 und 2, dadurch gekennzeichnet, daß in den allgemeinen Formeln II, III, IV der Wasserstoff in den Kohlenwasserstoffgruppen R1', R2', R3 ' und R4' teilweise oder gänzlich durch Halogen-, Nitro-, Nitroso-, Hydroxy-, Alkoxy-, Aryloxy-, Amino-, Amido-, Carboxyl-, Carbonyl-, Thio-, Sulfonyl- oder/und Metallocenylgruppen einfach oder mehrfach, gleich oder unabhängig voneinander verschieden ersetzt ist.Complex compound according to Claims 1 and 2, characterized in that, in the general formulas II, III, IV, the hydrogen in the hydrocarbon groups R 1 ' , R 2' , R 3 ' and R 4' is partially or entirely halogenated, nitro, Nitroso, hydroxy, alkoxy, aryloxy, amino, amido, carboxyl, carbonyl, thio, sulfonyl or / and metallocenyl groups singly or multiply, the same or independently different is set. Komplexverbindung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß in den allgemeinen Formeln II, III, IV R3' und R4' ein anneliertes Ringsystem darstellt.Complex according to one of claims 1 to 3, characterized in that in the general formulas II, III, IV R 3 ' and R 4' represents a fused ring system. Komplexverbindung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß L1 und L2 einen Chelatliganden der allgemeinen Formel V L1-Y-L2 Vausbilden, wobei L1 ein N-heterocyclisches Carbon der allgemeinen Formel II ist, wobei die mit Y bezeichneten Brückenglieder aus cyclischen, nicht cyclischen, geradkettigen oder/und verzweigten Resten aus der Gruppe von Alkylenresten mit 1 bis 50 Kohlenstoffatomen, Alkenylenresten mit 1 bis 50 Kohlenstoffatomen, Alkinylenresten mit 1 bis 50 Kohlenstoffatomen, Arylenresten mit 1 bis 30 Kohlenstoffatomen, Metallocenylen-, Borylen- und Silylenrestenbestehen, bei denen gegebenenfalls mindestens ein Wasserstoff durch Alkyl-, Aryl-, Alkenyl-, Alkinyl-, Metallocenyl-, Halogen-, Nitro-, Nitroso-, Hydroxo-, Alkoxy-, Aryloxy-, Amino-, Amido-, Carbonyl-, Carbonyl-, Thio- oder/und Sulfonylgruppen, bevorzugt durch Alkyl-, Aryl- oder/und Metallocenylgruppen einfach oder mehrfach, gleich oder unabhängig voneinander verschieden substituiert ist.Complex according to one of claims 1 to 4, characterized in that L 1 and L 2 a chelating ligand of the general formula V L 1 -YL 2 V wherein L 1 is an N-heterocyclic carbon of the general formula II, wherein the bridge members denoted by Y from cyclic, non-cyclic, straight-chain and / or branched radicals from the group of alkylene radicals having 1 to 50 carbon atoms, alkenylene radicals having 1 to 50 Carbon atoms, alkynylene radicals having from 1 to 50 carbon atoms, arylene radicals having from 1 to 30 carbon atoms, metallocenylene, borylene and silylene radicals in which optionally at least one hydrogen is substituted by alkyl, aryl, alkenyl, alkynyl, metallocenyl, halogen, nitro -, nitroso, hydroxo, alkoxy, aryloxy, amino, amido, carbonyl, carbonyl, thio or / and sulfonyl groups, preferably by alkyl, aryl or / and metallocenyl groups singly or multiply, the same or is independently substituted differently. Komplexverbindung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die Liganden der allgemeinen Formeln II, III, IV, oder/und V zentrale, axiale oder/und planare Chiralität aufweisen.Complex compound according to one of claims 1 to 5, characterized in that the Ligands of the general formulas II, III, IV, or / and V central, axial and / or planar chirality exhibit. Komplexverbindung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß in der allgemeinen Strukturformel I R1 bis R2 für Wasserstoff, substituierte oder/und nichtsubstituierte Alkyl-, Alkenyl- oder/und Arylreste stehen, daß X1 und X2 Halogenid-, Alkoxid- oder/und Carboxylationen sind oder/und daß L1 für ein N-heterozyklisches Carben der aligemeinen Formel II steht.Complex according to one of claims 1 to 6, characterized in that in the general structural formula IR 1 to R 2 are hydrogen, substituted or / and unsubstituted alkyl, alkenyl or / and aryl radicals, that X 1 and X 2 halide, Alkoxide and / or carboxylate ions are or / and that L 1 is an N-heterocyclic carbene of the general formula II. Verfahren zur Herstellung von acyclischen Olefinen mit zwei oder mehr Kohlenstoffatomen oder/und von cyclischen Olefinen mit vier oder mehr Kohlenstoffatomen jeweils entsprechend der allgemeinen Formel VI
Figure 00220001
aus acyclischen Olefinen mit zwei oder mehr Kohlenstoffatomen oder/und aus cyclischen Olefinen mit vier oder mehr Kohlenstoffatomen jeweils entsprechend der allgemeinen Formel VI durch Olefin-Metathese-Reaktion in Gegenwart mindestens eines Katalysators, dadurch gekennzeichnet, daß ein Katalysator nach einem der Ansprüche 1 bis 7 eingesetzt wird und daß R''1, R''2, R''3 und R''4 in der allgemeinen Formel VI für Wasserstoff oder/und Kohlenwasserstoffgruppen stehen, wobei die Kohlenwasserstoffgruppe aus gleich oder unabhängig voneinander verschieden geradkettigen, verzweigten, cyclischen oder/und nicht cyclischen Resten aus der Gruppe von Alkylresten mit 1 bis 50 Kohlenstoffatomen, Alkenylresten mit 1 bis 50 Kohlenstoffatomen, Alkinylresten mit 1 bis 50 Kohlenstoffatomen, Arylresten mit 1 bis 30 Kohlenstoffatomen, Metallocenyl- oder/und Silylresten besteht, wobei gegebenenfalls R''1, R''2, R''3 und R''4 für Halogen-, Nitro-, Nitroso-, Hxdroxy-, Alkoxy-, Aryloxy-, Amino-, Amido-, Carboxyl-, Carbonyl-, Thio-, Sulfonyl- oder/und Metallocenylgruppen einfach oder mehrfach, gleich oder unabhängig voneinander verschieden stehen.A process for the preparation of acyclic olefins having two or more carbon atoms or / and of cyclic olefins having four or more carbon atoms each corresponding to the general formula VI
Figure 00220001
from acyclic olefins having two or more carbon atoms and / or from cyclic olefins having four or more carbon atoms corresponding in each case to the general formula VI by olefin-metathesis reaction in the presence of at least one catalyst, characterized in that a catalyst according to one of claims 1 to 7 is used and that R '' 1 , R '' 2 , R '' 3 and R '' 4 in the general formula VI are hydrogen or / and hydrocarbon groups, wherein the hydrocarbon group from the same or independently different straight-chain, branched, cyclic or / and non-cyclic radicals from the group of alkyl radicals having 1 to 50 carbon atoms, alkenyl radicals having 1 to 50 carbon atoms, alkynyl radicals having 1 to 50 carbon atoms, aryl radicals having 1 to 30 carbon atoms, metallocenyl or / and silyl radicals, where appropriate R '' 1 , R'' 2 , R'' 3 and R'' 4 for halogen, nitro, nitroso, hydroxy, alkoxy, aryloxy, amino , Amido, carboxyl, carbonyl, thio, sulfonyl or / and metallocenyl groups singly or multiply, the same or independently different. Verfahren gemäß Anspruch 8 dadurch gekennzeichnet, daß R''1, R''2, R''3 und R''4 in den herzustellenden Olefinen der allgemeinen Formel VI paarweise, einfach oder mehrfach, gleich oder unabhängig voneinander verschieden einen Cyclus ausbilden. A method according to claim 8, characterized in that R '' 1 , R '' 2 , R '' 3 and R '' 4 in the olefins of general formula VI to be prepared in pairs, one or more times, the same or independently different form a cycle. Verfahren gemäß einem der Ansprüche 8 bis 9, dadurch gekennzeichnet, daß in den herzustellenden Olefinen der allgemeinen Formel VI der Wasserstoff in den Kohlenwasserstoffgruppen R''1, R''2, R''3 und R''4 teilweise oder gänzlich durch Halogen-, Silyl-, Nitro-, Nitroso-, Hydroxy-, Alkoxy-, Aryloxy-, Amino-, Amido-, Carboxyl-, Carbonyl-, Thio-, Sulfonyl- oder/und Metallocenylgruppen einfach oder mehrfach, gleich oder unabhängig voneinander verschieden ersetzt ist.Process according to one of Claims 8 to 9, characterized in that in the olefins of the general formula VI to be prepared the hydrogen in the hydrocarbon groups R " 1 , R" 2 , R " 3 and R" 4 is partly or wholly halogen , Silyl, nitro, nitroso, hydroxy, alkoxy, aryloxy, amino, amido, carboxyl, carbonyl, thio, sulfonyl or / and metallocenyl groups singly or multiply, the same or independently different is replaced. Verfahren nach einem der Ansprüche 8 bis 10, dadurch gekennzeichnet, daß der Prozeß mit oder ohne Lösungsmittel, jedoch vorzugsweise mit organischen Lösungsmitteln, durchgeführt wird.Method according to one of claims 8 to 10, characterized that the Process with or without solvents, however, preferably with organic solvents. Verfahren nach einem der Ansprüche 8 bis 11, dadurch gekennzeichnet, daß das Verfahren unter Zusatz einer Brönstedt-Säure, vorzugsweise von HCl, HBr, HI, HBF4, HPF6 oder/und Trifluoressigsäure, durchgeführt wird.Process according to one of Claims 8 to 11, characterized in that the process is carried out with the addition of a Bronsted acid, preferably of HCl, HBr, HI, HBF 4 , HPF 6 or / and trifluoroacetic acid. Verfahren nach einem der Ansprüche 8 bis 11, dadurch gekennzeichnet, daß das Verfahren unter Zusatz einer Lewis-Säure, vorzugsweise von BF3, AlCl3 oder/und ZnI2, durchgeführt wird.Process according to one of Claims 8 to 11, characterized in that the process is carried out with addition of a Lewis acid, preferably BF 3 , AlCl 3 or / and ZnI 2 .
DE19815275A 1998-04-06 1998-04-06 Alkylidene complexes of ruthenium with N-heterocyclic carbene ligands and their use as highly active, selective catalysts for olefin metathesis Expired - Lifetime DE19815275B4 (en)

Priority Applications (13)

Application Number Priority Date Filing Date Title
DE19815275A DE19815275B4 (en) 1998-04-06 1998-04-06 Alkylidene complexes of ruthenium with N-heterocyclic carbene ligands and their use as highly active, selective catalysts for olefin metathesis
DE59912097T DE59912097D1 (en) 1998-04-06 1999-03-18 ALKYLIDE COMPLEXES OF THE RUTHENIUM WITH N-HETEROCYCLIC CARBIGEN LIGANDS; USE AS CATALYSTS FOR THE OLEFIN METATHESIS
EP99910357A EP1087838B1 (en) 1998-04-06 1999-03-18 Alkylidene complexes of ruthenium with n-heterocyclic carbene ligands and their use as catalysts for olefin metathesis
PCT/EP1999/001785 WO1999051344A1 (en) 1998-04-06 1999-03-18 Alkylidene complexes of ruthenium with n-heterocyclic carbene ligands and their use as highly active, selective catalysts for olefin metathesis
US09/647,742 US6635768B1 (en) 1998-04-06 1999-03-18 Alkylidene complexes of ruthenium containing N-heterocyclic carbene ligands; use as highly active, selective catalysts for olefin metathesis
JP2000542103A JP4531253B2 (en) 1998-04-06 1999-03-18 Ruthenium alkylidene complexes containing N-heterocyclic carbene ligands; use as highly active selective catalysts for olefin metathesis
IL13859599A IL138595A (en) 1998-04-06 1999-03-18 Alkylidene complexes of ruthenium with n-heterocyclic carbene ligands and their use as highly active, selective catalysts for olefin metathesis
US10/630,552 US7294717B2 (en) 1998-04-06 2003-07-29 Alkylidene complexes of ruthenium containing N-heterocyclic carbene ligands; use as highly active, selective catalysts for olefin metathesis
US11/021,967 US7652145B2 (en) 1998-04-06 2004-12-23 Alkylidene complexes of ruthenium containing N-heterocyclic carbene ligands; use as highly active, selective catalysts for olefin metathesis
US11/828,828 US7378528B2 (en) 1998-04-06 2007-07-26 Alkylidene complexes of ruthenium containing N-heterocyclic carbene ligands; use as highly active, selective catalysts for olefin metathesis
US12/115,139 US20080207911A1 (en) 1998-04-06 2008-05-05 Alkylidene complexes of ruthenium containing n-heterocyclic carbene ligands; use as highly active, selective catalysts for olefin metathesis
US13/090,688 US8153810B2 (en) 1998-04-06 2011-04-20 Alkylidene complexes of ruthenium containing N-heterocyclic carbene ligands; use as highly active, selective catalysts for olefin metathesis
US14/193,785 US20150038723A1 (en) 1998-04-06 2014-02-28 Alkylidene complexes of ruthenium containing n-heterocyclic carbene ligands; use as highly active, selective catalysts for olefin metathesis

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19861474 1998-04-06
DE19815275A DE19815275B4 (en) 1998-04-06 1998-04-06 Alkylidene complexes of ruthenium with N-heterocyclic carbene ligands and their use as highly active, selective catalysts for olefin metathesis

Publications (2)

Publication Number Publication Date
DE19815275A1 DE19815275A1 (en) 1999-10-07
DE19815275B4 true DE19815275B4 (en) 2009-06-25

Family

ID=7863687

Family Applications (2)

Application Number Title Priority Date Filing Date
DE19815275A Expired - Lifetime DE19815275B4 (en) 1998-04-06 1998-04-06 Alkylidene complexes of ruthenium with N-heterocyclic carbene ligands and their use as highly active, selective catalysts for olefin metathesis
DE59912097T Expired - Lifetime DE59912097D1 (en) 1998-04-06 1999-03-18 ALKYLIDE COMPLEXES OF THE RUTHENIUM WITH N-HETEROCYCLIC CARBIGEN LIGANDS; USE AS CATALYSTS FOR THE OLEFIN METATHESIS

Family Applications After (1)

Application Number Title Priority Date Filing Date
DE59912097T Expired - Lifetime DE59912097D1 (en) 1998-04-06 1999-03-18 ALKYLIDE COMPLEXES OF THE RUTHENIUM WITH N-HETEROCYCLIC CARBIGEN LIGANDS; USE AS CATALYSTS FOR THE OLEFIN METATHESIS

Country Status (6)

Country Link
US (7) US6635768B1 (en)
EP (1) EP1087838B1 (en)
JP (1) JP4531253B2 (en)
DE (2) DE19815275B4 (en)
IL (1) IL138595A (en)
WO (1) WO1999051344A1 (en)

Families Citing this family (179)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19815275B4 (en) 1998-04-06 2009-06-25 Evonik Degussa Gmbh Alkylidene complexes of ruthenium with N-heterocyclic carbene ligands and their use as highly active, selective catalysts for olefin metathesis
US7285593B1 (en) 1998-05-19 2007-10-23 Advanced Polymer Technologies, Inc. Polyolefin compositions optionally having variable toughness and/or hardness
US7507854B2 (en) 1998-09-01 2009-03-24 Materia, Inc. Impurity reduction in Olefin metathesis reactions
US6696597B2 (en) 1998-09-01 2004-02-24 Tilliechem, Inc. Metathesis syntheses of pheromones or their components
US6900347B2 (en) 1998-09-01 2005-05-31 Tilliechem, Inc. Impurity inhibition in olefin metathesis reactions
EP2116302B1 (en) * 1998-09-10 2017-02-22 University Of New Orleans Foundation Catalyst complex with a heterocyclic carbene ligand
IL144549A0 (en) 1999-02-05 2002-05-23 Materia Inc Polyolefin compositions having variable density and methods for their production and use
US20140088260A1 (en) 1999-02-05 2014-03-27 Materia, Inc. Metathesis-active adhesion agents and methods for enhancing polymer adhesion to surfaces
WO2000046256A1 (en) 1999-02-05 2000-08-10 Advanced Polymer Technologies, Inc. Polyolefin compositions having enhanced ultraviolet and oxidative resistance and methods for their production and use
JP2002536468A (en) 1999-02-05 2002-10-29 マテリア インコーポレイテッド Metathesis-active adhesive and method for enhancing polymer adhesion to surfaces
US6426419B1 (en) * 1999-03-31 2002-07-30 California Institute Of Technology Ruthenium metal alkylidene complexes coordinated with triazolylidene ligands that exhibit high olefin metathesis activity
US7329758B1 (en) 1999-05-24 2008-02-12 California Institute Of Technology Imidazolidine-based metal carbene metathesis catalysts
EP2270063B1 (en) * 1999-05-31 2016-03-23 Zeon Corporation Process for producing hydrogenated product of cyclic olefin polymer prepared through ring-opening polymerization
CA2392049C (en) * 1999-11-18 2012-01-31 Richard L. Pederson Metathesis syntheses of pheromones or their components
TW593406B (en) * 1999-12-07 2004-06-21 Zeon Corp Copolymer formed by ring-opening polymerization, hydrogenation product of copolymer formed by ring-opening polymerization, and process for producing these
DE10014297A1 (en) 2000-03-23 2001-09-27 Merck Patent Gmbh Metathesis reaction of unsaturated organic compound, e.g. cyclization of octa-1,7-diene to cyclohexene, involves mixing and reacting compound and metathesis catalyst in liquid or dissolved form in microreactor
DE10015452A1 (en) 2000-03-29 2001-10-04 Bayer Ag Processes for the polymerization of polar substituted cycloalkenes, useful for optical applications, are carried out in the presence of at least one tungsten carbyne and/or molybdenum carbyne complex.
US7494927B2 (en) 2000-05-15 2009-02-24 Asm International N.V. Method of growing electrical conductors
WO2002000590A1 (en) * 2000-06-23 2002-01-03 California Institute Of Technology Synthesis of functionalized and unfunctionalized olefins via cross and ring-closing metathesis
JP2002020395A (en) * 2000-07-04 2002-01-23 Sekisui Chem Co Ltd New organometallic complex having high metathesis activity, metathesis reaction catalyst containing the same, polymerization method by using the catalyst, and resin composition obtained by the polymerization method
DE10064750A1 (en) * 2000-12-22 2002-06-27 Bayer Ag Production of 1,6-hexane diol for use in polyester or polyurethane production involves reacting formaldehyde with propene to form a homo-allyl alcohol, catalytic metathesis to 3-hexene-1,6-diol and catalytic hydrogenation
US6838489B2 (en) 2001-03-23 2005-01-04 Cymetech, Llc High activity metal carbene metathesis catalysts generated using a thermally activated N-heterocyclic carbene precursor
JP4226906B2 (en) * 2001-03-26 2009-02-18 ダウ グローバル テクノロジーズ インコーポレイティド Metathesis of unsaturated fatty acid esters or unsaturated fatty acids with lower olefins
WO2002079126A1 (en) * 2001-03-30 2002-10-10 California Institute Of Technology Cross-metathesis reaction of functionalized and substituted olefins using group 8 transition metal carbene complexes as metathesis catalysts
DE10137051A1 (en) 2001-07-31 2003-02-20 Bayer Ag New transition metal complexes with 2-alkoxybenzylidene ligands and hydrogenated imidazole ligands, useful as catalysts in metathesis reactions
JP2005508883A (en) 2001-08-01 2005-04-07 カリフォルニア　インスティチュート　オブ　テクノロジー Hexacoordinate ruthenium or osmium metal carbene metathesis catalyst
WO2003027079A1 (en) * 2001-09-20 2003-04-03 Zeon Corporation Ruthenium complexes, process for preparation thereof, and processes for producing open-ring polymers of cycloolefins and hydrogenation products thereof by using the complexes as catalyst
WO2003044060A2 (en) 2001-11-15 2003-05-30 Materia, Inc. Chelating carbene ligand precursors and their use in the synthesis of metathesis catalysts
KR20040111565A (en) 2002-04-29 2004-12-31 다우 글로벌 테크놀로지스 인크. Integrated chemical processes for industrial utilization of seed oils
DE10231368A1 (en) * 2002-07-11 2004-02-05 Studiengesellschaft Kohle Mbh Process for the preparation of imidazolium salts
US7002049B2 (en) 2002-08-19 2006-02-21 Eastman Chemical Company Process for α,β-dihydroxyalkenes and derivatives
US7094898B2 (en) * 2003-05-29 2006-08-22 University Of Ottawa Ruthenium compounds, their production and use
US7205424B2 (en) * 2003-06-19 2007-04-17 University Of New Orleans Research And Technology Foundation, Inc. Preparation of ruthenium-based olefin metathesis catalysts
BRPI0415176B1 (en) * 2003-10-09 2014-04-15 Dow Global Technologies Llc Process of preparation of an unsaturated alcohol and composition
CA2462011A1 (en) * 2004-02-23 2005-08-23 Bayer Inc. Process for the preparation of low molecular weight nitrile rubber
KR101162394B1 (en) 2004-02-23 2012-07-06 란세스 인크. Process for the preparation of low molecular weight nitrile rubber
EP1735352B1 (en) 2004-03-29 2019-08-21 California Institute Of Technology Latent, high-activity olefin metathesis catalysts containing an n-heterocyclic carbene ligand
AU2005252276B2 (en) 2004-06-09 2010-10-14 Uti Limited Partnership Transition metal carbene complexes containing a cationic substituent as catalysts of olefin metathesis reactions
FR2878246B1 (en) 2004-11-23 2007-03-30 Inst Francais Du Petrole PROCESS FOR CO-PRODUCTION OF OLEFINS AND ESTERS BY ETHENOLYSIS OF UNSATURATED FATTY BODIES IN NON-AQUEOUS IONIC LIQUIDS
US20060129013A1 (en) * 2004-12-09 2006-06-15 Abazajian Armen N Specific functionalization and scission of linear hydrocarbon chains
DE102004060247A1 (en) * 2004-12-15 2006-06-29 Studiengesellschaft Kohle Mbh New N-heterocyclic carbene radical compounds useful as e.g. catalysts in organocatalysis; and ligands in transition metal catalysts in homogeneous catalysis
US7666773B2 (en) 2005-03-15 2010-02-23 Asm International N.V. Selective deposition of noble metal thin films
US8025922B2 (en) 2005-03-15 2011-09-27 Asm International N.V. Enhanced deposition of noble metals
US8461223B2 (en) * 2005-04-07 2013-06-11 Aspen Aerogels, Inc. Microporous polycyclopentadiene-based aerogels
US7750149B2 (en) * 2005-04-11 2010-07-06 Wisconsin Alumni Research Foundation Seven-membered heterocyclic carbenes and their metal complexes
JP2006342212A (en) * 2005-06-07 2006-12-21 Kuraray Co Ltd Method for producing ring-opened metathesis polymer, and the resultant ring-opened metathesis polymer, and molded form obtained from the polymer
US20070014919A1 (en) * 2005-07-15 2007-01-18 Jani Hamalainen Atomic layer deposition of noble metal oxides
JP5522941B2 (en) 2005-12-16 2014-06-18 マテリア， インコーポレイテッド Process for the production of organometallic ruthenium complexes and related tetrasubstituted and other bulky olefins
FR2896500B1 (en) * 2006-01-24 2010-08-13 Inst Francais Du Petrole PROCESS FOR CO-PRODUCTION OF OLEFINS AND DIESTERS OR DIACIDES BY HOMOMETATHESIS OF UNSATURATED FATTY BODIES IN NON-AQUEOUS IONIC LIQUIDS
US20070225536A1 (en) * 2006-03-23 2007-09-27 Eugene Frederick Lutz Olefin conversion process and olefin recovery process
US7435484B2 (en) * 2006-09-01 2008-10-14 Asm Japan K.K. Ruthenium thin film-formed structure
AR066191A1 (en) 2007-03-22 2009-08-05 Schering Corp PROCESS AND INTERMEDIARIES FOR THE SYNTHESIS OF COMPOUNDS 8- [(1- (3,5- BIS- (TRIFLUOROMETIL) PHENYL) - ETOXI) - METAL] - 8 PHENYL - 1,7- DIAZA - ESPIRO (4, 5) DECAN - 2 ONA
DE102007018148A1 (en) 2007-04-16 2008-10-23 Evonik Degussa Gmbh Preparation of alkene, which is a polymer compound, preferably homopolymer, copolymer or block-copolymer, comprises metathesis reaction of unsaturated compound containing an alkene or alkyne unit in the presence of an active catalyst
DE102007020694A1 (en) 2007-05-03 2008-11-06 Evonik Degussa Gmbh Sulfur-containing metathesis catalysts
ES2569483T3 (en) 2007-06-21 2016-05-11 Amgen Inc. Methods to synthesize cinacalcet and salts thereof
US20090087339A1 (en) * 2007-09-28 2009-04-02 Asm Japan K.K. METHOD FOR FORMING RUTHENIUM COMPLEX FILM USING Beta-DIKETONE-COORDINATED RUTHENIUM PRECURSOR
US8241575B2 (en) 2008-01-28 2012-08-14 The Johns Hopkins University Molecularly imprinted polymer sensor device
WO2009124977A1 (en) † 2008-04-08 2009-10-15 Evonik Degussa Gmbh Method for manufacturing ruthenium carbene complexes
EP2147721A1 (en) * 2008-07-08 2010-01-27 Lanxess Deutschland GmbH Catalyst systems and their use in metathesis reactions
EP2157076A1 (en) * 2008-08-21 2010-02-24 Cognis IP Management GmbH Process for the preparation of unsaturated alpha, omega dicarboxylic acid diesters
US8084104B2 (en) * 2008-08-29 2011-12-27 Asm Japan K.K. Atomic composition controlled ruthenium alloy film formed by plasma-enhanced atomic layer deposition
PT2346823E (en) 2008-09-05 2015-11-26 Opko Health Inc Intermediates for the synthesis of 8-[{1-(3,5-bis-(trifluoromethyl)phenyl)-ethoxy}-methyl]-8-phenyl-1,7-diaza-spiro[4.5]decan-2-one compounds
JP2012503025A (en) 2008-09-22 2012-02-02 エルロン・セラピューティクス・インコーポレイテッド Method for preparing a purified polypeptide composition
WO2010051268A1 (en) * 2008-10-31 2010-05-06 Dow Global Technologies Inc. Olefin metathesis process employing bimetallic ruthenium complex with bridging hydrido ligands
CN102227489B (en) * 2008-11-26 2015-04-15 埃莱文斯可更新科学公司 Methods of producing jet fuel from natural oil feedstocks through oxygen-cleaved reactions
CA2742374C (en) * 2008-11-26 2016-10-04 Elevance Renewable Sciences, Inc. Methods of producing jet fuel from natural oil feedstocks through metathesis reactions
FR2939331B1 (en) 2008-12-10 2012-08-10 Inst Francais Du Petrole CATALYTIC COMPOSITION AND METHOD FOR THE METATHESIS OF UNSATURATED BODY
US9379011B2 (en) 2008-12-19 2016-06-28 Asm International N.V. Methods for depositing nickel films and for making nickel silicide and nickel germanide
DE102009005951A1 (en) 2009-01-23 2010-07-29 Evonik Degussa Gmbh Aldehyde-functional compounds
EP2210870A1 (en) 2009-01-23 2010-07-28 Evonik Degussa GmbH Hydroxy and aldehyde functional connections
MX2011011742A (en) * 2009-05-05 2011-12-08 Stepan Co Sulfonated internal olefin surfactant for enhanced oil recovery.
US20110020546A1 (en) * 2009-05-15 2011-01-27 Asm International N.V. Low Temperature ALD of Noble Metals
US9222056B2 (en) 2009-10-12 2015-12-29 Elevance Renewable Sciences, Inc. Methods of refining natural oils, and methods of producing fuel compositions
US8735640B2 (en) 2009-10-12 2014-05-27 Elevance Renewable Sciences, Inc. Methods of refining and producing fuel and specialty chemicals from natural oil feedstocks
US9175231B2 (en) 2009-10-12 2015-11-03 Elevance Renewable Sciences, Inc. Methods of refining natural oils and methods of producing fuel compositions
US9051519B2 (en) 2009-10-12 2015-06-09 Elevance Renewable Sciences, Inc. Diene-selective hydrogenation of metathesis derived olefins and unsaturated esters
US9382502B2 (en) 2009-10-12 2016-07-05 Elevance Renewable Sciences, Inc. Methods of refining and producing isomerized fatty acid esters and fatty acids from natural oil feedstocks
US8957268B2 (en) 2009-10-12 2015-02-17 Elevance Renewable Sciences, Inc. Methods of refining natural oil feedstocks
US9000246B2 (en) 2009-10-12 2015-04-07 Elevance Renewable Sciences, Inc. Methods of refining and producing dibasic esters and acids from natural oil feedstocks
US9365487B2 (en) 2009-10-12 2016-06-14 Elevance Renewable Sciences, Inc. Methods of refining and producing dibasic esters and acids from natural oil feedstocks
US9169447B2 (en) 2009-10-12 2015-10-27 Elevance Renewable Sciences, Inc. Methods of refining natural oils, and methods of producing fuel compositions
WO2011059803A2 (en) * 2009-10-29 2011-05-19 Board Of Regents, The University Of Texas System Ruthenium-alkylidenes containing acyclic diaminocarbenes for obtaining low e/z ratios in cross metathesis
GB201004732D0 (en) 2010-03-22 2010-05-05 Univ Aberdeen Ruthenium complexes for use in olefin metathesis
US9403781B2 (en) 2010-04-27 2016-08-02 The Regents Of The University Of California Crystalline 1H-1,2,3-triazol-5-ylidenes
US9452568B2 (en) 2010-08-23 2016-09-27 Materia, Inc. VARTM flow modifications for low viscosity resin systems
EP2428269A1 (en) 2010-09-08 2012-03-14 Bergen Teknologioverføring AS Novel olefin metathesis catalysts
US8871617B2 (en) 2011-04-22 2014-10-28 Asm Ip Holding B.V. Deposition and reduction of mixed metal oxide thin films
WO2012166259A2 (en) * 2011-05-31 2012-12-06 Exxonmobil Chemical Patents Inc. A novel class of olefin metathesis catalysts, methods of preparation, and processes for the use thereof
US8524930B2 (en) 2011-05-31 2013-09-03 Exxonmobil Chemical Patents Inc. Class of olefin metathesis catalysts, methods of preparation, and processes for the use thereof
BR112013032369B1 (en) 2011-06-17 2021-08-24 Materia, Inc RESIN COMPOSITION, METHOD TO IMPROVE THE ADHESION OF SUCH RESIN COMPOSITION AND USE OF AT LEAST ONE ADHESION PROMOTER
WO2013007561A1 (en) 2011-07-12 2013-01-17 Basf Se Process for preparing cycloheptene
US8993819B2 (en) 2011-07-12 2015-03-31 Basf Se Process for preparing cycloheptene
US9181360B2 (en) 2011-08-12 2015-11-10 Exxonmobil Chemical Patents Inc. Polymers prepared by ring opening / cross metathesis
GB201116719D0 (en) * 2011-09-28 2011-11-09 Univ St Andrews Ruthenium polymerisation catalysts
FR2983475B1 (en) * 2011-12-02 2014-01-17 IFP Energies Nouvelles PROCESS FOR THE METATHESIS OF ALPHA LINEAR OLEFINS USING AN RUTHENIUM COMPLEX COMPRISING A DISSYMETRIC N-HETEROCYCLIC CARBENE
US9169174B2 (en) 2011-12-22 2015-10-27 Elevance Renewable Sciences, Inc. Methods for suppressing isomerization of olefin metathesis products
US9133416B2 (en) 2011-12-22 2015-09-15 Elevance Renewable Sciences, Inc. Methods for suppressing isomerization of olefin metathesis products
US9139493B2 (en) 2011-12-22 2015-09-22 Elevance Renewable Sciences, Inc. Methods for suppressing isomerization of olefin metathesis products
WO2013136111A2 (en) 2012-03-13 2013-09-19 Invista Technologies S.A R.L. Nylon polymer and process
NZ701296A (en) 2012-04-24 2016-02-26 Stepan Co Unsaturated fatty alcohol alkoxylates from natural oil metathesis
CA2871428A1 (en) 2012-04-24 2013-10-31 Elevance Renewable Sciences, Inc. Unsaturated fatty alcohol compositions and derivatives from natural oil metathesis
BR112014026539B1 (en) 2012-04-24 2021-06-01 Stepan Company SULFATE DERIVATIVE, SULFATE COMPOSITION, PROCESS TO PREPARE A SULFATE COMPOSITION
US8940940B2 (en) 2012-06-13 2015-01-27 Basf Se Process for preparing macrocyclic ketones
JP2015523440A (en) 2012-06-20 2015-08-13 エレヴァンス リニューアブル サイエンシズ インコーポ Natural oil metathesis composition and method thereof
US9234985B2 (en) 2012-08-01 2016-01-12 California Institute Of Technology Birefringent polymer brush structures formed by surface initiated ring-opening metathesis polymerization
WO2014022482A1 (en) 2012-08-01 2014-02-06 California Institute Of Technology Solvent-free enyne metathesis polymerization
WO2014055720A1 (en) * 2012-10-05 2014-04-10 California Institute Of Technology Photoinitiated olefin metathesis polymerization
US9388098B2 (en) 2012-10-09 2016-07-12 Elevance Renewable Sciences, Inc. Methods of making high-weight esters, acids, and derivatives thereof
FR2999185B1 (en) * 2012-12-12 2015-01-02 Ecole Nationale Superieure De Chimie De Rennes PROCESS FOR THE METATHESIS OF ALPHA LINEAR OLEFINS USING AN RUTHENIUM COMPLEX COMPRISING AN UNSATURATED DISSYMETRIC N-HETEROCYCLIC DIAMINOCARBENE
US9527982B2 (en) 2012-12-19 2016-12-27 Materia, Inc. Storage stable adhesion promoter compositions for cyclic olefin resin compositions
FR3002161B1 (en) * 2013-02-21 2015-12-18 IFP Energies Nouvelles FISCHER-TROPSCH CUT OLEFINE METATHESIS METHOD USING RUTHENIUM COMPLEX COMPRISING SYMMETRIC N-HETEROCYCLIC DIAMINOCARBENE
US9598531B2 (en) 2013-02-27 2017-03-21 Materia, Inc. Olefin metathesis catalyst compositions comprising at least two metal carbene olefin metathesis catalysts
EP2961778A4 (en) 2013-02-27 2016-10-05 Materia Inc Metal carbene olefin metathesis two catalyst composition
EP2778154A1 (en) * 2013-03-13 2014-09-17 Evonik Industries AG In situ generation of ruthenium catalysts for olefin metathesis
WO2014159211A1 (en) 2013-03-14 2014-10-02 Elevance Renewable Sciences, Inc. Alkenyl glycosides and their preparation
JP6342985B2 (en) 2013-03-15 2018-06-13 マテリア， インコーポレイテッド In-mold coating of ROMP polymer
WO2014153406A1 (en) 2013-03-20 2014-09-25 Elevance Renewable Sciences, Inc. Acid catalyzed oligomerization of alkyl esters and carboxylic acids
US9663440B2 (en) 2013-04-09 2017-05-30 Materia, Inc. Cross metathesis of poly-branched poly-olefins
JP6188925B2 (en) * 2013-05-24 2017-08-30 アランセオ・ドイチュランド・ゲーエムベーハー Ruthenium complexes, their preparation and use as catalysts
WO2014198022A1 (en) * 2013-06-09 2014-12-18 Lanxess Deutschland Gmbh Ruthenium- or osmium-based complex catalysts
EP3013886A4 (en) 2013-06-24 2016-08-31 Materia Inc Thermal insulation
CN105492489B (en) 2013-07-03 2017-06-13 马特里亚公司 Liquid mold composition
US9890239B2 (en) 2013-09-04 2018-02-13 California Institute Of Technology Functionalized linear and cyclic polyolefins
JP6273749B2 (en) * 2013-10-04 2018-02-07 国立大学法人山口大学 Network polymers and polymer gel electrolytes
WO2015065649A1 (en) 2013-10-30 2015-05-07 California Institute Of Technology Direct photopatterning of robust and diverse materials
EP3092204A4 (en) 2014-01-10 2017-12-20 Materia, Inc. Method and composition for improving adhesion of metathesis compositions to substrates
US10907018B2 (en) 2014-02-27 2021-02-02 Materia, Inc. Adhesion promoter compositions for cyclic olefin resin compositions
US10000601B2 (en) 2014-03-27 2018-06-19 Trent University Metathesized triacylglycerol polyols for use in polyurethane applications and their related properties
WO2015143562A1 (en) 2014-03-27 2015-10-01 Trent University Metathesized triacylglycerol green polyols from palm oil for use in polyurethane applications and their related physical properties
CA2981087A1 (en) 2014-03-27 2015-10-01 Trent University Certain metathesized natural oil triacylglycerol polyols for use in polyurethane applications and their related physical properties
US9592476B2 (en) 2014-05-30 2017-03-14 Pall Corporation Membrane comprising self-assembled block copolymer and process for producing the same by hybrid casting (IIb)
US9598543B2 (en) 2014-05-30 2017-03-21 Pall Corporation Self-assembled structure and membrane comprising block copolymer and process for producing the same by spin coating (VIa)
US9592477B2 (en) 2014-05-30 2017-03-14 Pall Corporation Membrane comprising self-assembled block copolymer and process for producing the same by hybrid casting (Ib)
US9604181B2 (en) 2014-05-30 2017-03-28 Pall Corporation Membrane comprising self-assembled block copolymer and process for producing the same by spray coating (IIc)
US9162189B1 (en) 2014-05-30 2015-10-20 Pall Corporation Membrane comprising self-assembled block copolymer and process for producing the same by spin coating (Ia)
US9163122B1 (en) 2014-05-30 2015-10-20 Pall Corporation Self-assembling polymers—II
US9469733B2 (en) 2014-05-30 2016-10-18 Pall Corporation Self-assembled structure and membrane comprising block copolymer and process for producing the same by spin coating (IVa)
US9193835B1 (en) 2014-05-30 2015-11-24 Pall Corporation Self-assembling polymers—IV
US9169361B1 (en) 2014-05-30 2015-10-27 Pall Corporation Self-assembling polymers—VI
US9765171B2 (en) 2014-05-30 2017-09-19 Pall Corporation Self-assembling polymers—V
US9593219B2 (en) 2014-05-30 2017-03-14 Pall Corporation Membrane comprising self-assembled block copolymer and process for producing the same by spin coating (IIa)
US9616395B2 (en) 2014-05-30 2017-04-11 Pall Corportaion Membrane comprising self-assembled block copolymer and process for producing the same by spray coating (Ic)
US9441078B2 (en) 2014-05-30 2016-09-13 Pall Corporation Self-assembling polymers—I
US9328206B2 (en) 2014-05-30 2016-05-03 Pall Corporation Self-assembling polymers—III
US9593218B2 (en) 2014-05-30 2017-03-14 Pall Corporation Self-assembled structure and membrane comprising block copolymer and process for producing the same by spin coating (IIIa)
US9593217B2 (en) 2014-05-30 2017-03-14 Pall Corporation Self-assembled structure and membrane comprising block copolymer and process for producing the same by spin coating (Va)
US9309367B2 (en) 2014-06-30 2016-04-12 Pall Corporation Membranes comprising cellulosic material and hydrophilic block copolymer (V)
US9260569B2 (en) 2014-06-30 2016-02-16 Pall Corporation Hydrophilic block copolymers and method of preparation thereof (III)
US9962662B2 (en) 2014-06-30 2018-05-08 Pall Corporation Fluorinated polymer and use thereof in the preparation of hydrophilic membranes (vi)
US9394407B2 (en) 2014-06-30 2016-07-19 Pall Corporation Hydrophilic block copolymers and membranes prepared therefrom (I)
US9718924B2 (en) 2014-06-30 2017-08-01 Pall Corporation Hydrophilic block copolymers and membranes prepared therefrom (II)
US9303133B2 (en) 2014-06-30 2016-04-05 Pall Corporation Hydrophilic membranes and method of preparation thereof (IV)
US9254466B2 (en) 2014-06-30 2016-02-09 Pall Corporation Crosslinked cellulosic membranes
CN107107462A (en) 2014-10-21 2017-08-29 斯特拉塔西斯公司 Use the three-dimensional ink-jet printing method of ring-opening metathesis polymerization
US9777245B2 (en) 2015-01-30 2017-10-03 Trent University Methods of fractionating metathesized triacylglycerol polyols and uses thereof
WO2016130743A1 (en) 2015-02-12 2016-08-18 Materia, Inc. Cyclic olefin resin compositions comprising functional elastomers
CN107250202B (en) 2015-02-14 2021-10-01 马特里亚公司 ROMP polymers with improved resistance to hydrocarbon fluids
EP3115368A1 (en) 2015-07-10 2017-01-11 Bergen Teknologioverforing AS Improved olefin metathesis catalysts
EP3124580A1 (en) 2015-07-31 2017-02-01 Total Marketing Services Branched diesters for use to reduce the fuel consumption of an engine
EP3124579A1 (en) 2015-07-31 2017-02-01 Total Marketing Services Lubricant composition comprising branched diesters and viscosity index improver
JP7013370B2 (en) 2015-09-24 2022-01-31 ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト Metal carbene olefin metathesis catalyst
US9607842B1 (en) 2015-10-02 2017-03-28 Asm Ip Holding B.V. Methods of forming metal silicides
MX2018006241A (en) 2015-11-18 2018-11-09 Provivi Inc Production of fatty olefin derivatives via olefin metathesis.
BR112018010108A2 (en) 2015-11-18 2018-11-21 Provivi Inc microorganisms for the production of insect pheromones and related compounds
US11001725B2 (en) 2016-02-05 2021-05-11 Stratasys Ltd. Three-dimensional inkjet printing using ring-opening metathesis polymerization
EP3411424B1 (en) 2016-02-05 2024-01-10 Stratasys Ltd. Three-dimensional inkjet printing using polyamide-forming materials
WO2017134673A1 (en) 2016-02-07 2017-08-10 Stratasys Ltd. Three-dimensional printing combining ring-opening metathesis polymerization and free radical polymerization
US11118004B2 (en) 2016-04-26 2021-09-14 Stratasys Ltd. Three-dimensional inkjet printing using ring-opening metathesis polymerization
WO2017214133A2 (en) 2016-06-06 2017-12-14 Provivi, Inc. Semi-biosynthetic production of fatty alcohols and fatty aldehydes
EP3496855B1 (en) 2016-08-15 2023-01-18 Umicore Ag & Co. Kg Metathesis catalysts
EP3500557A4 (en) * 2016-08-19 2020-03-18 Umicore Ag & Co. Kg Olefin metathesis catalysts
EP4194092A1 (en) 2016-08-24 2023-06-14 Umicore AG & Co. KG Synthesis and characterization of metathesis catalysts
EP3515885B1 (en) 2016-09-23 2023-12-13 Umicore Ag & Co. Kg Preparation of amino acids and amino acid derivatives
WO2018213554A1 (en) 2017-05-17 2018-11-22 Provivi, Inc. Microorganisms for the production of insect pheromones and related compounds
US11471867B2 (en) * 2017-06-23 2022-10-18 Gwangju Institute Of Science And Technology Ligand for forming ruthenium complex, ruthenium complex catalyst, production method therefor and use thereof
FR3075802B1 (en) 2017-12-22 2020-11-20 Demeta CYCLOOLEFIN POLYMERIZATION PROCESS BY METATHESIS WITH CYCLE OPENING
EP3546495A1 (en) 2018-03-29 2019-10-02 Evonik Degussa GmbH Method for producing temperature-stable polyalkenamers
US10995049B2 (en) 2019-07-19 2021-05-04 California Institute Of Technology Total synthesis of prostaglandin J natural products and their intermediates
US20240124809A1 (en) 2022-10-03 2024-04-18 The Goodyear Tire & Rubber Company Reactor cleaning process and composition

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5312940A (en) * 1992-04-03 1994-05-17 California Institute Of Technology Ruthenium and osmium metal carbene complexes for olefin metathesis polymerization
WO1996004289A1 (en) * 1992-04-03 1996-02-15 California Institute Of Technology High activity ruthenium or osmium metal carbene complexes for olefin metathesis reactions and synthesis thereof
DE4447066A1 (en) * 1994-12-29 1996-07-04 Hoechst Ag Metal complex compounds containing heterocyclic carbenes
WO1997006185A1 (en) * 1995-08-03 1997-02-20 California Institute Of Technology High metathesis activity ruthenium and osmium metal carbene complexes
WO1997034875A1 (en) * 1996-03-20 1997-09-25 Celanese Gmbh Process for preparing heterocyclic carbenes
WO2000058322A1 (en) * 1999-03-31 2000-10-05 California Institute Of Technology Novel ruthenium metal alkylidene complexes coordinated with triazolylidene ligands that exhibit high olefin metathesis activity
US20020137978A1 (en) * 2000-06-23 2002-09-26 Grubbs Robert H. Synthesis of functionalized and unfunctionalized olefins via cross and ring-closing Metathesis

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19815275B4 (en) 1998-04-06 2009-06-25 Evonik Degussa Gmbh Alkylidene complexes of ruthenium with N-heterocyclic carbene ligands and their use as highly active, selective catalysts for olefin metathesis
DE19902439A1 (en) * 1999-01-22 2000-08-03 Aventis Res & Tech Gmbh & Co Homo- and heterobimetallic alkylidene complexes of ruthenium with N-heterocyclic carbene ligands and their use as highly active, selective catalysts for olefin metathesis
US7329758B1 (en) * 1999-05-24 2008-02-12 California Institute Of Technology Imidazolidine-based metal carbene metathesis catalysts
US7241898B2 (en) * 2003-08-02 2007-07-10 Boehringer Ingelheim International Gmbh Metathesis catalysts
WO2005016522A1 (en) * 2003-08-11 2005-02-24 Merck Patent Gmbh Immobilizable ruthenium catalysts having n-heterocyclic carbene ligands
EP1654064A2 (en) * 2003-08-11 2006-05-10 MERCK PATENT GmbH Immobilised imidazoles and ruthenium catalysts
EP1735352B1 (en) * 2004-03-29 2019-08-21 California Institute Of Technology Latent, high-activity olefin metathesis catalysts containing an n-heterocyclic carbene ligand
AU2005252276B2 (en) * 2004-06-09 2010-10-14 Uti Limited Partnership Transition metal carbene complexes containing a cationic substituent as catalysts of olefin metathesis reactions

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5312940A (en) * 1992-04-03 1994-05-17 California Institute Of Technology Ruthenium and osmium metal carbene complexes for olefin metathesis polymerization
WO1996004289A1 (en) * 1992-04-03 1996-02-15 California Institute Of Technology High activity ruthenium or osmium metal carbene complexes for olefin metathesis reactions and synthesis thereof
DE4447066A1 (en) * 1994-12-29 1996-07-04 Hoechst Ag Metal complex compounds containing heterocyclic carbenes
WO1997006185A1 (en) * 1995-08-03 1997-02-20 California Institute Of Technology High metathesis activity ruthenium and osmium metal carbene complexes
WO1997034875A1 (en) * 1996-03-20 1997-09-25 Celanese Gmbh Process for preparing heterocyclic carbenes
WO2000058322A1 (en) * 1999-03-31 2000-10-05 California Institute Of Technology Novel ruthenium metal alkylidene complexes coordinated with triazolylidene ligands that exhibit high olefin metathesis activity
US20020137978A1 (en) * 2000-06-23 2002-09-26 Grubbs Robert H. Synthesis of functionalized and unfunctionalized olefins via cross and ring-closing Metathesis

Non-Patent Citations (15)

* Cited by examiner, † Cited by third party
Title
C.P. Köcher, Dissertation, TUM, 1996, München, S. 124-137, Jahrbuch der TUM S 568. und Originaldokument *
Enders et al.: "Immobilized Triazolium Salts as Precursors to Chiral Carbenes - Rhodium-Catalyzed Asymrnetric Hydrosilyation as a First Test Reaction", Molecules Online, 1998, 2, 105-108, 09. Juli 1998 http://www.springerlink.com/content/nnn9j6d7qZd1p0 c/ fulltext.pdf, heruntergeladen am 12.09.2007) *
H. Clavier et al. Chem Eurj. 2007, received February 13, 2007 *
Herrmann et al.:"N-Heterocyclic Carbenes", Angew. Chem. Int. Ed. Engl., 1997, 36(20), 2162-2187, XP2178612 *
Herrmann:"N-Heterocyclic Carbenes: A New Concept in Organometallic Catalysis" ,Angew. Chem. Int. Ed., 2002, 41 (8), 1290-1309, XP1111697 *
J. Huang et al. JMCS, 1999, 121, 26742678, voraus veröffentlicht im Internet 11. März 1999 *
L. Ackermann et al., Tetrahedron Letters 40 (1999) 4787-4790 *
M. Scholl et al., Tetrahedron Letters 40 (1999) 2247-2250 *
M. Schuster, S. Blechert, Amgew. Chem. 1997, 109, 2124-2144 *
M. Ulmann et al., J. org. Chem. 1999, 64, 7202-7207 *
T. Weskamp et al., Angew. Chem. Int. Ed. 1999, 38 No 16, 2416- 2419 *
W.A. Herrmann, C. Köcher, Angew. Chem. 1997, 109, 2256-2282 *
W.C. Schattenmann, Dissertation, TUM, 1997, München, Jahrbuch der TUM S 580 und Originaldokument *
W.C. Schattenmann, Dissertation, TUM, 1997, München, Jahrbuch der TUM S 580 und Originaldokument C.P. Köcher, Dissertation, TUM, 1996, München, S. 124-137, Jahrbuch der TUM S 568. und Originaldokument W.A. Herrmann, C. Köcher, Angew. Chem. 1997, 109, 2256-2282 M. Schuster, S. Blechert, Amgew. Chem. 1997, 109, 2124-2144 T. Weskamp et al., Angew. Chem. Int. Ed. 1999, 38 No 16, 2416- 2419 H. Clavier et al. Chem Eurj. 2007, received February 13, 2007 J. Huang et al. JMCS, 1999, 121, 26742678, voraus veröffentlicht im Internet 11. März 1999 M. Ulmann et al., J. org. Chem. 1999, 64, 7202-7207 L. Ackermann et al., Tetrahedron Letters 40 (1999) 4787-4790 M. Scholl et al., Tetrahedron Letters 40 (1999) 2247-2250 Herrmann et al.:"N-Heterocyclic Carbenes", Angew. Chem. Int. Ed. Engl., 1997, 36(20), 2162-2187, XP2178612 Herrmann:"N-Heterocyclic Carbenes: A New Concept in Organometallic Catalysis" ,Angew. Chem. Int. Ed., 2002, 41 (8), 1290-1309, XP1111697 Weskamp: "N-heterocyclische Carbene: Eine n
Weskamp: "N-heterocyclische Carbene: Eine neue Generation von Rutheniumkatalysatoren für die Olefin-Metathese", Dissertation, technische Universität München, 11.05.1999 (Datum der Annahme durch Fakultät) *

Also Published As

Publication number Publication date
JP4531253B2 (en) 2010-08-25
WO1999051344A1 (en) 1999-10-14
US7652145B2 (en) 2010-01-26
EP1087838A1 (en) 2001-04-04
US8153810B2 (en) 2012-04-10
US20050107626A1 (en) 2005-05-19
US20080207911A1 (en) 2008-08-28
US7378528B2 (en) 2008-05-27
US7294717B2 (en) 2007-11-13
IL138595A0 (en) 2001-10-31
US6635768B1 (en) 2003-10-21
DE59912097D1 (en) 2005-06-30
US20040095792A1 (en) 2004-05-20
US20110282068A1 (en) 2011-11-17
US20050013150A2 (en) 2005-01-20
IL138595A (en) 2004-08-31
JP2002510658A (en) 2002-04-09
EP1087838B1 (en) 2005-05-25
DE19815275A1 (en) 1999-10-07
US20080009598A1 (en) 2008-01-10
US20150038723A1 (en) 2015-02-05

Similar Documents

Publication Publication Date Title
DE19815275B4 (en) Alkylidene complexes of ruthenium with N-heterocyclic carbene ligands and their use as highly active, selective catalysts for olefin metathesis
EP1022282B1 (en) Homo- and hetero metal alkylidene complexes of ruthenium with N-heterocyclic carbene ligands, and their use as highly active and selective catalysts for olefin metathesis
DE69631769T2 (en) RUTHENIUM AND OSMIUM METAL COLOR COMPLEXES HAVING HIGH METATHESE ACTIVITY
Suzuki et al. Selective carbon-carbon bond cleavage of cyclopentadiene on a trinuclear ruthenium pentahydride complex
EP2260047B2 (en) Method for manufacturing ruthenium carbene complexes
EP1031553B1 (en) Process for the preparation of substituted olefins
CA2312755A1 (en) Highly active cationic ruthenium and osmium complexes for olefin metathesis reactions
EP1005476B1 (en) Method for producing ruthenium complexes
WO2011026809A1 (en) Chiral metal complexes, and use thereof as a catalyst for organic compound synthesis
DE60206262T2 (en) NEW METHOD FOR THE PRODUCTION OF METAL CARBIDE COMPLEXES
DE10039389A1 (en) Ruthenium complexes containing carbenoids
Arena et al. Half-sandwich ruthenium (II) and rhodium (III) complexes bearing chiral amino-phosphoramidite ligands: Synthesis, characterization and application in asymmetric transfer hydrogenation of acetophenone
WO2012085013A1 (en) Method for the ethenolysis of polyterpenes and decomposition products obtainable therefrom
WO2008101683A2 (en) Fe(-II) CATALYST SYSTEMS
Ru et al. CLUSTER CHEMISTRY
DE19642278A1 (en) Alcohol and aldehyde preparation with good selectivity
EP2436681A1 (en) Derivatisation of hydroxyacetale and hydroxyacetale mixtures

Legal Events

Date Code Title Description
8127 New person/name/address of the applicant

Owner name: DEGUSSA AG, 40474 DUESSELDORF, DE

8110 Request for examination paragraph 44
8127 New person/name/address of the applicant

Owner name: DEGUSSA GMBH, 40474 DUESSELDORF, DE

8127 New person/name/address of the applicant

Owner name: EVONIK DEGUSSA GMBH, 40474 DUESSELDORF, DE

8172 Supplementary division/partition in:

Ref document number: 19861474

Country of ref document: DE

Kind code of ref document: P

Q171 Divided out to:

Ref document number: 19861474

Country of ref document: DE

Kind code of ref document: P

AH Division in

Ref document number: 19861474

Country of ref document: DE

Kind code of ref document: P

8364 No opposition during term of opposition
R071 Expiry of right